Synthesis of 2-sulfonyl indenes and indanes

Article abstract of DOI:10.1021/acs.joc.9b01606

In this paper, we developed facile and high-yield synthetic routes for the preparation of 2-sulfonyl indenes and indanes, including: (i) Amberlyst-15-promoted Knoevenagel reaction of β-ketosulfones and arylaldehydes in refluxing toluene; (ii) Grignard reagent (R′MgBr) or reducing reagent (NaBH₄) promoted regio-and/or stereocontrolled 1,4-Addition or 1,4-/1,2-reduction of the resulting sulfonyl chalcones in THF or MeOH/THF at 25 °C; and then (iii) Amberlyst-15 mediated intramolecular Friedel-Crafts annulation of the corresponding β-ketosulfones or β-hydroxysulfones in toluene at reflux. This present method describes a highly efficient (3 + 2) annulation via the formation of two carbon-carbon (C-C) bonds. The DFT calculations were utilized to rationalize the regioselectivity of the addition reaction.

Full text of DOI:10.1021/acs.joc.9b01606

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Article
Synthesis of 2-Sulfonyl Indenes and Indanes
Meng-Yang Chang, Yan-Shin Wu, Yu-Lin Tsai, and Hsing-Yin Chen
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.9b01606 • Publication Date (Web): 29 Aug 2019
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Page 1 of 30
The Journal of Organic Chemistry
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Synthesis of 2-Sulfonyl Indenes and Indanes
Meng-Yang Chang,*a,b Yan-Shin Wu,a Yu-Lin Tsaia and Hsing-Yin Chen*a
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aDepartment of Medicinal and Applied Chemistry, Kaohsiung Medical University, Kaohsiung 807, Taiwan bDepartment of
Medical Research, Kaohsiung Medical University Hospital, Kaohsiung 807, Taiwan
*Email: mychang@kmu.edu.tw; hychen@kmu.edu.tw
O
2
O
R
O
O
O
R
R
S
S
S
Amberlyst 15
NaBH then
4
O
O
O
+
Ar
Ar
Amberlyst 15
Amberlyst 15
Ar
Ar'
O
Ar'
O
R'
O
Ar'
R'MgBr
O
2
R'
R
R
S
S
O
O
Ar
Ar
Ar'
Ar'
ABSTRACT: In this paper, we developed facile and high-yield synthetic routes for the preparation of 2-sulfonyl indenes and in-
danes, including: (i) Amberlyst 15-promoted Knoevenagel reaction of β-ketosulfones and arylaldehydes in refluxing toluene; (ii)
Grignard reagent (R’MgBr) or reducing reagent (NaBH4) promoted regio- and/or stereocontrolled 1,4-addition or 1,4-/1,2-reduction
of the resulting sulfonyl chalcones in THF or MeOH/THF at 25 °C; then, (iii) Amberlyst 15 mediated intramolecular Friedel-Crafts
annulation of the corresponding -ketosulfones or -hydroxysulfones in toluene at reflux. This present method describes a highly
efficient (3+2) annulation via the formation of two carbon-carbon (C-C) bonds. The DFT calculations were utilized to rationalize
the regioselectivity of the addition reaction.
Introduction
mide,17 (iv) Cu+ promoted sulfonylation of indene with di-
methyl sulfoxide in the presence of an oxygen atmosphere,18 (v)
Pd2+ promoted remote ortho C-H alkenylation of arylethyl 2-
pyridyl sulfone followed by base mediated intramolecular ring-
closure19 and (vi) electrooxidative tandem cyclization of acti-
vated alkynes with sulfinic acid.20 Although diversified routes
have been described to construct sulfonyl indanes or indenes, it
still remains challenging to explore a facile and high-yield
method in the formation of this core system.
Indane and indene ring structures with a benzofused bicyclic
ring system are important skeleton units in diversified natural
products, functionalized building blocks, biological active
molecules, and drug candidates.1-3 The development of new
methodologies to provide access to these diversified indane and
indene derivatives has steadily increased according to recent
reports. Many considerable attempts have been evaluated to
determine versatile synthetic routes, including: (1) Brønsted
(TfOH, Tf2NH)4 or Lewis acid (Ph3CB(C6F5)4, BF3·OEt2,
Ca(NTf2)2, In(OTf)3)5 mediated inter- or intramolecular
Friedel-Crafts type ring-closure and (2) metal complex (Al,6
Pd,7 Rh,8 Rh/Ag,9 Rh,10 Rh/Mn,11 Cu,12 Fe,13 or Ni14) catalysed
inter- or intramolecular carboannulation. There are various
methods described in the literature for the efficient synthesis of
substituted indanes or indenes via tandem coupling/annulation
modes, but there are only limited reports for the synthesis of
sulfonyl indanes or indenes.15-20 The sulfonyl group represents
one of the most important organic functionalities and is found
in many biologically active compounds and synthetic interme-
diates. Therefore, the incorporation of the sulfonyl group into
organic molecules is an important task.21-27
Scheme 1. Typical Routes of 2-Sulfonyl Indanes and Indenes
electrooxidative cycliztion
(ref 20)
condensation / ring-closure
(this work)
O
O
R
O
Ph
O
S
S
O
+
+
OH
Ph
Ar
Ar'
O
_
Amberlyst 15
Pt (+) / Pt ( )
SO Ph
2
N
S
O
2
O
R
R
O
S
Ph
+
S
S
2
Pd(II)
then
O
O
O
Ar
Ar
base
oxidation (ref 15)
o-alkenylation/
annulation (ref 19)
Ir(I)
t-BuLi
Cu(I), O
Me
O
2
S
O
Tol
O
O
S
Br
Et
MeO C
2
Me
S
O
In Scheme 1, the typical routes for the synthesis of 2-
sulfonyl indanes and indenes include: (i) oxidation of 2-indanyl
phenyl sulfide,15 (ii) Ir+ catalysed [2+2+2] cycloaddition of
sulfonyl diyne and monoyne,16 (iii) base-mediated conjugation
of tosylmethyl isocyanide (TosMIC) and 2-bromobenzyl bro-
Ph
+
Me
+
+
N
Br
sulfonylation
(ref 18)
[2+2+2] cycloaddition
(ref 16)
isocyanide-cyanide
rearrangement (ref 17)
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Page 2 of 30
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Herein, we describe easy-operational and high-yield syn-
tions in mind, we turned our attention to A-15. It is a
thetic routes for Amberlyst 15-promoted syntheses of 2-
sulfonyl arylindenes and arylindanes.28 To the best of our
knowledge, there have been no reports for an acidic solid sup-
port mediated synthesis of indenes and indanes via (3+2) annu-
lation fashion via the recyclable heterogeneous catalytic proce-
dure. Commercially available Amberlyst-15 (abbreviated as A-
15, an ion exchange resin with a strongly acidic sulfonic group)
is now routinely applied in organic synthesis as an environ-
mentally benign reusable heterogeneous catalyst in functional
group transformations of various molecules.29-32
macroreticular polystyrene-based ion exchange solid support
with a strongly acidic sulfonic group.39 By using A-15 (1.0 g),
the yield of 4a was increased to 92% (entry 14). To decrease
the weight (1.0  0.5  0.1 g), high yields were maintained
by using the Dean-Stark apparatus (entries 15-16). Entry 17
showed that once recovered A-15 (0.1 g) also provided 4a in an
85% yield. Twice recovered A-15 (0.1 g) provided 4a in low
yield (40%, entry 18). However, when recovered A-15 (0.1 g)
was used three times, only a trace amount (5%) of 4a was ob-
served. Therefore, we believe that A-15 is an optimal acidic
promoter because it is required in catalytic amounts, is safe to
operate, and is readily removed at the end of the reaction.
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Results and Discussion
In continuation with our investigation efforts in the synthetic
researches of β-ketosulfones,33-38 we investigated synthetic
routes towards 2-sulfonyl arylindenes 1 and arylindanes 2,
including (i) A-15-promoted Knoevenagel reaction of β-
ketosulfones 5 and arylaldehydes 6 in toluene, (ii) R’MgBr or
NaBH4-mediated regio- and/or stereochemical 1,4-addition of
1,4-/1,2-reduction of the resulting sulfonyl (E)-chalcones 4 in
MeOH, THF or MeOH/THF and (iii) A-15 mediated sequential
intramolecular Friedel-Crafts annulation of substituted β-
ketosulfones 3 or -hydroxysulfones 7, as shown in Scheme 2.
Table 1. Reaction Conditionsa
O
O
O
Tol
acidic
conditions
Tol
S
S
OMe
OMe
OMe
OMe
O
O
+
Ph
O
Ph
O
5a
6a
4a
b
entry reagent (equiv or g) solvent time (h) temp (oC)
%
c-e
1
2
3
4
5
6
7
8
9
p-TsOH (1 equiv) toluene
p-TsOH (1 equiv) toluene
p-TsOH (1 equiv) toluene
p-TsOH (1 equiv) toluene
p-TsOH (1 equiv) CHCl3
p-TsOH (1 equiv) benzene
p-TsOH (1 equiv) xylene
p-TsOH (0.1 equiv) toluene
p-TsOH (0.5 equiv) toluene
20
20
3
25
─
─
c-e
111
111
111
61
35f
32f
21f
30f
32f
85f
68f
33f
80f
46f-g
25f-g
92f
92f
92f
85f
40f
20
3
Scheme 2. Retrosynthetic Route of Indenes 1 and Indanes 2
1,4-addition or
Knoevenagel condensation
Friedel-Crafts annulation
1,4- / 1,2-reduction
1
3
80
O
R
R
R'
O
R
S
O
R
S
O
A-15
A-15
S
3
145
111
111
111
111
111
111
111
111
111
111
111
O
O
Ar
Ar
R'MgBr
Ar'
Ar'
O
3
O
3
R
Ar'
O
O
S
A-15
indene 1
5
O
Ar
3
O
S
R
+
O
R
Ar'
O
S
O
10 p-TsOH (1.5 equiv) toluene
11 MsOH (0.1 equiv) toluene
12 TfOH (0.1 equiv) toluene
13 Tf2NH (0.1 equiv) toluene
3
O
4
NaBH
4
Ar
Ar
Ar
Ar'
indane 2
Ar'
OH
7
3
6
3
The initial work began with the reaction of two model com-
pounds, 5a (Ar’ = Ph, R = Tol, 0.5 mmol) and 6a (Ar = 3,4-
(MeO)2Ph, 0.6 mmol), with p-TsOH (0.5 mmol) in toluene at
25 °C and reflux for 20 h, respectively, in the presence of
MgSO4 (200 mg) under an open-vessel condition. However, no
reaction was observed (Table 1, entries 1-2). Using a Dean-
Stark distillation apparatus, 4a was isolated in a 35% yield
after reflux for 3 h (entry 3). After elongating the reaction (3 
10 h), a similar yield (32%) of 4a was observed (entry 4). By
the removal of water, the yield of 4a was slightly increased.
After adjusting the solvent from toluene to CHCl3, only 21% of
4a was obtained (entry 5). In entries 6-7, other solvents (e.g.,
benzene and xylene) could not enhance the yield of 4a. Next,
catalytic and stoichiometric amounts of p-TsOH were exam-
ined. In entries 10-13, the use of 0.1, 0.5 and 1.5 equiv of p-
TsOH gave 4a in 89%, 68% and 33% yields, respectively (en-
tries 8-10). From the results, we found that catalytic amounts
(0.1 equiv) provided better yields of 4a (85%) than other
stoichiometric amounts. Possible reasons for this could be that
excess protons triggered the intermediate of β-hydroxysulfone
to cause the retro-aldol process to occur easily, thus inhibiting
the dehydration pathway, and two starting materials, 5a and 6a,
were recovered as major products under Brønsted acid medi-
ated Knoevenagel condensation. Other commercially available
sulfonic acids were screened next (entries 11-13). We found
that the catalytic amounts of MsOH, TfOH and Tf2NH could
not enhance the yield of 4a due to the stronger acidity resulting
in the formation of a complex mixture. With these considera-
3
14 A-15 (1.0 g)
15 A-15 (0.5 g)
16 A-15 (0.1 g)
17 A-15 (0.1 g)h
18 A-15 (0.1 g)i
toluene
toluene
toluene
toluene
toluene
3
3
3
3
3
aReactions were performed using a 0.5 mmol scale with 5a, 6a
(1.2 equiv), solvent (10 mL). Isolated yields. cMgSO4 (0.2 g)
b
d
e
f
was added. No reactions. Open-vessel condition. Dean-Stark
apparatus. Major complex mixture was obtained. Recovered
g
h
A-15 was used. iTwice recovered A-15 was used.
To study the substrate scope of A-15 mediated Knoevenagel
condensation, substituted 5 and 6 were reacted in toluene to
afford diversified 4 by the optimal conditions established (Ta-
ble 1, entry 16). As shown in Table 2, the facile formation of
4a-4ai showed that the R and Ar’ substituents of 5a-5p and the
Ar substituent of 6a-6y did not influence the yield (entries 1-
41). However, 4s, having a tricyclic bulky group (Ar = 9-
anthracyl), was not produced (from 5a and 6s, entry 19).
Among these substrates, 4ai (Ar = 2-NO2C6H4, entry 35), 4al
(Ar = 2-pyridyl, entry 38) and 4am (Ar = 2-furyl, entry 39)
provided lower yields (72%, 68% and 64%). For the electronic
character of the Ar’ substituents of 4, electron-neutral, electron
withdrawing, and electron-donating groups were suitable. For
the R substituent of 4, both aliphatic and aromatic sulfonyl
groups were appropriate. For the Ar substituent of 6, electron-
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The Journal of Organic Chemistry
neutral, donating and withdrawing and heterocyclic groups
Furthermore, phenylacetaldehyde was examined, but no de-
2
3
4
5
were also well-tolerated. For the structural framework of all
isolated 4, only the (E)-isomer was observed. The structure of
4n was determined by single-crystal X-ray analysis.40
Table 2. Synthesis of 4a-b
sired product was detected. We think that these abovemen-
tioned reaction conditions could make the cross-aldol coupling
of aldehydes and β-ketosulfones occur easily, which could
allow a complex mixture to be formed. Another attempt to
adjust the carbonyl synthon from aldehyde to ketone was
evaluated. However, no reaction was observed for the A-15
catalysed condensation of 5a and acetophenone. Overall, the
present condition would only be suitable for the arylaldehyde
group.
6
O
O
O
R
R
2
7
8
S
S
Amberlyst 15
toluene
3
4
O
O
+
Ar
Ar
Ar'
O
Ar'
O
4
5
5
6
9
entry 5, R =, Ar’ =
6, Ar =
4, %b
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
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29
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33
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1
2
3
4
5
6
7
8
9
5a, Tol, Ph
5a, Tol, Ph
5a, Tol, Ph
5a, Tol, Ph
5a, Tol, Ph
5a, Tol, Ph
5a, Tol, Ph
5a, Tol, Ph
5a, Tol, Ph
6a, 3,4-(MeO)2C6H3
6b, 3,4-CH2O2C6H3
6c, 3-MeOC6H4
4a, 92
4b, 95
4c, 96
4d, 93
4e, 93
4f, 94
4g, 90
4h, 96
4i, 95
4j, 94
4k, 93
4l, 92
4m, 94
4n, 90
4o, 90
Scheme 3. Synthesis of 3a-3an
R'
O
O
R
R
2
2
S
S
3
4
R'MgBr, THF
reflux, 10 h
3
4
O
O
Ar
Ar
Ar'
O
4
Ar'
O
3
6d, 4-MeOC6H4
5
5
6e, 3,4,5-(MeO)3C6H2
6f, Ph
R'
O
O
O
Tol
Tol
Tol
S
S
S
6g, 2-naphthyl
6h, 4-ClC6H4
6i, 3,4-Cl2C6H3
6j, 4-FC6H4
OMe
OMe
OMe
OMe
O
O
O
Ar
Ph
O
Ph
O
Ar'
O
3a, Ar = Ph (86%)
3j, R' = Ph (73%)
3r, Ar' = 4-FC H (82%)
3s, Ar' = 4-MeC H (84%)
6
4
3b, Ar = 4-MeOC H (85%)
3k, R' = 4-FC H (72%)
6
4
6
4
6 4
3c, Ar = 4-MeC H (80%)
3l, R' = 4-MeOC H (70%) 3t, Ar' = 4-MeOC H (80%)
6
4
6
4
6
4
10 5a, Tol, Ph
11 5a, Tol, Ph
12 5a, Tol, Ph
13 5a, Tol, Ph
14 5a, Tol, Ph
15 5a, Tol, Ph
16 5a, Tol, Ph
17 5a, Tol, Ph
18 5a, Tol, Ph
19 5a, Tol, Ph
20 5b, Tol, 4-FC6H4
3d, Ar = 4-FC H (83%)
3m, R' = 4-MeC H (74%) 3u, Ar' = 4-CF C H (86%)
6 4 3 6 4
6
4
3e, Ar = 4-PhC H (79%)
3n, R' = 2-MeC H (67%)
3v, Ar' = 4-PhC H (85%)
3w, Ar' = 2-naphthyl (82%)
6
4
6
4
6 4
6k, 2-BrC6H4
6l, 3-NO2C6H4
6m, 4-HOC6H4
6n, 4-PhC6H4
6o, 4-MeC6H4
3f, Ar = 2-naphthyl (78%)
3o, R' = Me (63%)
3g, Ar = 3,4-(MeO) C H (80%) 3p, R' = iPr (80%)
2
6 3
3h, Ar = 3,4-CH O C H (82%) 3q, R' = cC H (83%)
2
2
6
3
5
9
3i, Ar = 3,4,5-(MeO) C H (78%)
3
6 2
O
R
R'
O
O
Tol
S
S
O
O
Ar
Ar
O
R
Ph
O
Ph
Ar = Ph,
S
OMe
OMe
R = Tol
O
3ah, Ar = 2-NBn-pyrrolyl (80%)
3ai, Ar = 2-pyridyl (82%)
3aj, Ar = 2-furyl (80%)
R = Ph
3ak, Ar = 2-thienyl (86%)
R = Tol
3al, R' = 2-benzofuryl (83%)
3am, R' = 2-benzothienyl (80%)
3an, R' = 2-allyl-3,4-(MeO) C H (72%)
6p, 2-allyl-3,4-(MeO)2C6H2 4p, 83
3ad, R' = 4-FC H (74%)
Ph
O
6
4
Ar = 2-thienyl,
3ae, R' = cC H (75%)
6q, 3-pyridyl
4q, 80
4r, 84
4s, ─c
3x, R = Ph (80%)
3y, R = Me (78%)
6 11
3af, R' = cC H (78%)
5
9
3ag, R' = iPr (80%)
6r, 2-thienyl
3z, R = 4-MeOC H (74%)
6
4
3aa, R = 4-FC H (82%)
6
4
3ab, R = 4-iPrC H (85%)
6s, 9-anthracyl
6a, 3,4-(MeO)2C6H3
6 4
3ac, R = 4-nBuC H (82%)
6
4
2 6 3
4t, 98
With the above experimental results in hand, we shifted the
synthetic aim to investigate the conjugate addition of sulfonyl
chalcones 4 with the use of different Grignard reagents
(Scheme 3). Initially, by controlling the R and Ar’ group on 4
as the Tol and Ph, the cC6H11MgBr-mediated 1,4-addition of 4
with diversified Ar group provided 3a-3l in modest to good
yields (78%-86%). For the Ar group, electron-neutral groups
(Ph, Tol, biphenyl, naphthyl), an electron-withdrawing group
(4-FC6H4) and electron-donating mono-, di- or tri-oxygenated
groups were appropriate. Then, the R’ group was changed from
cyclohexyl to different aromatic and aliphatic groups, and 3j-
3q were produced in lower yields (63%-83%) by the conjugate
addition of 4a. For the R’ group, the aromatic groups (Ph, 4-
FC6H4, 4-MeOC6H4, 4-MeC6H4, 2-MeC6H4) provided slightly
higher yields than the aliphatic groups (Me, iPr, cC5H9).
Among them, the 2-MeC6H4 group afforded 3n at a low yield
(67%) due to the steric hindrance of the ortho-methyl group. In
particular, Me with a smaller group also provided a low yield
(63%) of 3o. Following, when the Ar’ group was changed to
other aromatic groups, 3r-3w were obtained in good yields
(80%-86%) via the Grignard addition of 4t-4w and 4y-4z with
cC6H11MgBr. Furthermore, adjusting the R group to methyl
and other aromatic groups, 3z-3ad were isolated with yields in
a range from 74%-85%. Since Ar became a heterocycle, the
monocycles (2-thienyl, 2-NBn-pyrrolyl, 2-pyridyl, 2-furyl) and
bicycles (2-benzofuryl and 2-benzothienyl) provided 3ae-3am
in 75%-86% yields. Additionally, 3an with an allylaryl moiety
was generated in a 72% yield. The results showed that treat-
21 5c, Tol, 4-MeOC6H4 6a, 3,4-(MeO)2C6H3
22 5d, Tol, Tol 6a, 3,4-(MeO)2C6H3
4u, 97
4v, 95
23 5e, Tol, 4-CF3C6H4 6a, 3,4-(MeO)2C6H3
24 5f, Tol, 4-NO2C6H4 6a, 3,4-(MeO)2C6H3
25 5g, Tol, 4-PhC6H4 6a, 3,4-(MeO)2C6H3
26 5h, Tol, 2-naphthyl 6a, 3,4-(MeO)2C6H3
4w, 92
4x, 90
4y, 90
4z, 92
27 5i, Ph, Ph
6a, 3,4-(MeO)2C6H3
6a, 3,4-(MeO)2C6H3
4aa, 90
4ab, 96
4ac, 96
4ad, 94
4ae, 93
4af, 96
4ag, 96
4ah, 96
4ai, 72
4aj, 80
4ak, 84
4al, 68
4am, 64
4an, 84
4ao, 78
28 5j, 4-FC6H4, Ph
29 5k, 4-MeOC6H4, Ph 6a, 3,4-(MeO)2C6H3
30 5l, 4-EtC6H4, Ph 6a, 3,4-(MeO)2C6H3
31 5m, 4-tBuC6H4, Ph 6a, 3,4-(MeO)2C6H3
32 5n, Me, Ph
33 5o, nBu, Ph
6a, 3,4-(MeO)2C6H3
6a, 3,4-(MeO)2C6H3
34 5p, Tol, 3,4-Cl2C6H3 6f, Ph
35 5a, Tol, Ph
36 5a, Tol, Ph
37 5i, Ph, Ph
38 5a, Tol, Ph
39 5a, Tol, Ph
40 5a, Tol, Ph
41 5a, Tol, Ph
6t, 2-NO2C6H4
6u, 2-NBn-pyrrolyl
6r, 2-thienyl
6v, 2-pyridyl
6w, 2-furyl
6x, 2-benzofuryl
6y, 2-benzothienyl
aReactions were performed using a 0.5 mmol scale with 5, 6
(1.2 equiv), A-15 (0.1 g), toluene (10 mL), reflux, 3 h. bIsolated
yields. cNo reaction.
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2
ment of 4 with different Grignard reagents generated diversi-
We also calculated the 1,2- and 1,4-adducts derived from the
fied Michael adducts. Among these products, no 1,2-adducts
were detected. For comparison between the 1,2-addition and
1,4-addition, DFT calculations were applied to provide a rea-
sonable explanation for the regiospecificity of the addition
reaction of 4.
reaction of 4a and the cC5H9MgBr Grignard reagent (Figure 2).
The 1,4-adduct (3q) was found to be substantially more stable
than the 1,2-adduct by 15 kcal/mol, which is in line with the
experimental observation that no 1,2-adduct was detected. The
natural steric analysis showed that the steric repulsion in the
1,2-adduct is significantly greater than that in the 1,4-adduct;
the steric exchange energies are 2468.3 and 2390.2 kcal/mol
for the 1,2- and 1,4-adducts, respectively. These results suggest
that the stability of these adducts; thus, the regioselectivity of
the addition reaction are determined by the steric effect.
3
4
5
6
7
8
9
Two conformations were found for 4a (Figure 1). One was
the closed conformation in which the toluene ring on the sul-
fonyl group and the phenyl ring on the carbonyl group formed
a -stacked arrangement; the - distance (centroid to centroid)
was 3.94 Å and the torsional angle (centroid-S-C-centroid) was
approximately 15. It can be clearly seen in this structure that
the carbon atom of the carbonyl group is well shielded by the
toluene and (MeO)2C6H3 rings; therefore, the 1,2-addition is
expected to be sterically hindered. By contrast, the carbon atom
of the =CH bridging group is exposed and in a less crowded
environment, rendering the 1,4-addition more favourable in
terms of steric consideration. The other conformation was an
open form in which the toluene ring and the phenyl ring
pointed in opposite directions; the torsional angle was 110.
Although in this structure the carbonyl group is not protected
by the toluene ring, the environment of the carbonyl group was
still somewhat crowded due to the presence of the sulfonyl
group (S=OC=O distance is 2.91 Å ). Furthermore, this open
conformation was 2 kcal/mol higher than the closed conforma-
tion and should be the minor form.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Scheme 4. Synthesis of 3ao-3as
O
O
Tol
Tol
2
S
S
3
4
NaBH , THF / MeOH
4
O
O
Ar
Ar
then PCC, CH Cl
Ar'
O
2
(yields of two-steps)
2
Ar'
O
5
4a-4b, 4e, 4w-4x
Ar' = Ph
3ao, Ar = 3,4-(MeO) C H (90%)
2 6 3
3ap, Ar = 3,4-CH O C H (86%)
6 2
2
3aq, Ar = 3,4,5-(MeO) C H (90%)
2 6 3
3
Ar = 3,4-(MeO) C H
3 6 4
3as, Ar' = 4-NO C H (90%)
2 6 3
3ar, Ar' = 4-CF C H (84%)
2
6 4
On the other hand, by adjusting the R’ group from aliphatic
and aromatic to hydride, the reduction of sulfonyl chalcones 4
was examined (Scheme 4). When R’MgBr was changed to
NaBH4, we found that a sequential 1,4- and then a 1,2-
reduction process occurred to generate -hydroxysulfones by
the use of 4a-4b, 4e and 4w-4x. The tandem reduction proce-
dure has been described in our previous report.41 Then, oxida-
tion of the resulting -hydroxysulfones with PCC provided
3ao-3as in 84%-90% yields of a two-step process. Overall,
skeleton 3 could be prepared with good yields and was utilized
as the precursor for the formation of indenes.
Figure 1. DFT Optimized Structures of 4a. The Relative Free
Energy (in kcal/mol) is Given in Parenthesis.
Scheme 5. Synthesis of 1a-1z
'
R'
O
O
R
R
R
S
S
Amberlyst 15
O
O
2
Ar
toluene
reflux, 10 h
3
Ar
Ar'
O
3
Ar'
5
4
1
'
O
O
O
R
Tol
Tol
Tol
S
S
S
O
O
O
Ar
Ph
Ph
Ar'
OMe
OMe
1d, R' = Ph (89%)
OMe
OMe
1i, Ar' = 4-FC H (92%)
1a, Ar = 3,4-(MeO) C H (90%)
2
6
2
6 4
1b, Ar = 3,4-CH O C H (86%)
1e, R' = 4-FC H (85%)
1j, Ar' = 4-MeC H (90%)
2
2
6
2
6
4
6 4
1c, Ar = 3,4,5-(MeO) C H (90%)
1f, R' = 4-MeOC H (92%)
1k, Ar' = 4-MeOC H (93%)
6 4
3
6
6
4
1g, R' = iPr (74%)
1l, Ar' = 4-CF C H (89%)
3 6 4
1h, R' = cC H (86%)
1m, Ar' = 4-PhC H (85%)
6 4
5
9
1n, Ar' = 2-naphthyl (86%)
O
Figure 2. DFT Optimized Structures of 1,2- and 1,4-Adducts
from 4a + cC5H9MgBr Reaction (for 3q). The Relative Free
Energy (in kcal/mol) is Given in Parenthesis.
R
S
O
Tol
O
O
Tol
S
S
O
O
Me
Ph
OMe
Ar
Ar'
O
Ph
1u (80%)
OMe
1o, R = Ph (88%)
1p, R = Me (90%)
1q, R = 4-MeOC H (91%)
1r, R = 4-FC H (92%)
1s, R = 4-iPrC H (86%)
Ar' = Ph,
1v, Ar = 3,4-(MeO) (78%)
OMe
2
6
4
1w, Ar = 3,4-CH O (74%)
2
2
6
4
1x, Ar = 3,4,5-(MeO) (83%)
3
6
4
Ar = 3,4-(MeO) C H
2
6 2
1t, R = 4-nBuC H (86%)
6
4
1y, Ar' = 4-CF C H (82%)
3
6 4
1z, Ar' = 4-NO C H (75%)
2
6 4
On the basis of these experimental results, we focused on the
construction of sulfonyl indenes 1 by A-15 mediated in-
tramolecular Friedel-Crafts annulation of skeleton 3. First, the
reaction of 3a was treated with A-15 under the above Dean-
Stark distillation. However, no desired indene skeleton was
isolated and only starting material 3a was recovered. For the
A-15 mediated reaction of 3b-3f, no reactions were observed
until Ar was introduced with an oxygenated aromatic group,
then intramolecular Friedel-Crafts annulation could be trig-
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gered (Scheme 5). The resulting phenomenon suggested that
(Ar’ = 4-CF3C6H4) and 2x (Ar’ = 4-NO2C6H4), the efficient
2
formation of sulfonyl arylindane 2 showed that the R, Ar’ and
Ar substituents did not influence the changes of yield (entries
1~34). For the R substituent of 4, both the aliphatic and aro-
matic sulfonyl groups were appropriate. For entries 9, 12, 17,
22 and 23, only 7i, 7l, 7q, 7w and 7x were afforded in excellent
yields, and the desired skeleton 2 with the indane ring was not
observed. After elongating the reaction time (3  60 h), the
results were unchanged.
the electron-donating oxygenated group enrich the -electron
density of the reaction system to trigger intramolecular ring-
closure. Furthermore, 1a-1c (Ar = 3,4-(MeO)2C6H2, 3,4-
CH2O2C6H2, 3,4,5-(MeO)3C6H) were obtained in good yields
(90%, 86%, 90%) via the A-15 mediated ring-closure of 3g-3i
at reflux for 10 h. Changing the R’ group formed a cyclohexyl
group to the aromatic (R’ = Ph, 4-FC6H4, 4-MeOC6H4) and
aliphatic (R’ = iPr, cC5H9) groups; 1d-1h were obtained in
74%-92% yields. After adjusting the Ar’ from phenyl to other
aromatic groups, 1i-1n were isolated in yields ranging from
85%-93%. Next, changing the R group to methyl and other
aromatic groups, 1o-1t were isolated in yields ranging from
86%-92%. By controlling the Ar = 3,4-(MeO)C6H2 and R’ =
cC6H11, different Ar’ and R substituents were well-tolerated in
maintaining good yields for the formation of skeleton 1. Fur-
thermore, when 3an was reacted with A-15, a tricyclic indeno-
fused dihydrofuran 1u was isolated at an 80% yield via in-
tramolecular Friedel-Crafts annulation. After replacing the R’
group with hydrogen, the A-15 mediated ring-closure of 3ao-
3as was examined. Under the reaction conditions, 1v-1z were
produced in modest to good (74%-83%) yields. Although the
Ar group on substrate 3 was limited to the oxygenated aryl
group, it still provided a novel and efficient transformation
from -arylketones to indenes. The molecular structures of 1a,
1e, 1h, 1q and 1z were determined by single-crystal X-ray
analysis.40
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Table 3. Synthesis of 2a
O
O
O
R
R
R
2
S
S
S
Amberlyst 15
toluene
NaBH
4
3
O
O
O
Ar
Ar
4
THF / MeOH
(v / v = 1 / 1)
Ar
Ar'
O
4
Ar'
OH
Ar'
5
7
2
entry 4, R =, Ar1 =, Ar =
2, %b
1
4a, Tol, Ph, 3,4-(MeO)2C6H3
4b, Tol, Ph, 3,4-CH2O2C6H3
4c, Tol, Ph, 3-MeOC6H4
4d, Tol, Ph, 4-MeOC6H4
4e, Tol, Ph, 3,4,5-(MeO)3C6H2
4f, Tol, Ph, Ph
2a, 84
2b, 86
2c, 88
2d, 86
2e, 91
2f, 84
2
3
4
5
6
7
4g, Tol, Ph, 2-naphthyl
4h, Tol, Ph, 4-ClC6H4
4i, Tol, Ph, 3,4-Cl2C6H3
4j, Tol, Ph, 4-FC6H4
2g, 86
2h, 83
2i, ─c
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
2j, 88
As an extension of A-15 mediated Knoevenagel condensa-
tion protocol, the synthesis of indane 2 was explored. Initially,
treatment of 4a with NaBH4 in THF-MeOH (1:1) at 25 °C for 3
h produced 7a (R = Tol, Ar’ = Ph) in a nearly quantitative yield
(Scheme 6). The procedure possessed a regioselective 1,4-
reduction of 4a followed by a stereoselective 1,2-reduction of
the corresponding ketone A. Because the isolated yield was
high, crude 7a was reacted with A-15 without further purifica-
tion. By the facile route, 2a was obtained in an 84% yield via
intramolecular Friedel-Crafts type annulation. According to the
Felkin-Anh model,41 the effect of steric hindrance on the sul-
fonyl group could inhibit the carbonyl reduction such that the
hydride attacked the carbonyl with less-repulsion face to yield
7a via a possible intermediate B, which is completed by the A-
15-chelated complexation of a hydroxyl motif on 7a. Participa-
tion of the oxygenated arene led to 2a via one methoxy group-
promoted intramolecular stereocontrolled SN2 para-addition on
intermediate C (see blue arrow).
4k, Tol, Ph, 2-BrC6H4
4l, Tol, Ph, 3-NO2C6H4
4m, Tol, Ph, 4-HOC6H4
4n, Tol, Ph, 4-PhC6H4
4o, Tol, Ph, 4-MeC6H4
2k, 87
2l, ─c
2m, 86
2n, 84
2o, 82
2p, 80
2q, ─c
2r, 80
2t, 82
4p, Tol, Ph, 2-allyl-3,4-(MeO)2C6H2
4q, Tol, Ph, 3-pyridinyl
4r, Tol, Ph, 2-thienyl
4t, Tol, 4-FC6H4, 3,4-(MeO)2C6H3
4u, Tol, 4-MeOC6H4, 3,4-(MeO)2C6H3
4v, Tol, 4-MeC6H4, 3,4-(MeO)2C6H3
4w, Tol, 4-CF3C6H4, 3,4-(MeO)2C6H3
4x, Tol, 4-NO2C6H4, 3,4-(MeO)2C6H3
4y, Tol, 4-PhC6H4, 3,4-(MeO)2C6H3
4z, Tol, 2-naphthyl, 3,4-(MeO)2C6H3
4aa, Ph, Ph, 3,4-(MeO)2C6H3
2u, 82
2v, 82
2w, ─c
2x, ─c
2y, 86
2z, 87
2aa, 87
2ab, 88
2ac, 86
2ad, 84
2ae, 86
2af, 89
2ag, 85
2ah, 82
Scheme 6. Plausible Mechanism
less repulsion face
1,4-reduction
1,2-reduction
OMe
4ab, 4-FC6H4, Ph, 3,4-(MeO)2C6H3
4ac, 4-MeOC6H4, Ph, 3,4-(MeO)2C6H3
4ad, 4-EtC6H4, Ph, 3,4-(MeO)2C6H3
4ae, 4-tBuC6H4, Ph, 3,4-(MeO)2C6H3
4af, Me, Ph, 3,4-(MeO)2C6H3
H
OMe
OMe
O
Tol
O
Tol
H
S
S
OMe
NaBH
4
O
O
O
O
Ph
BH
3
THF / MeOH
S
Ph
O
OMe
Ph
O
A
OMe
O
o
25 C, 3 h
Tol
4a
B
Felkin-Anh model
Friedel-Crafts annulation
H
O
O
Tol
O O
Tol
H
4ag, nBu, Ph, 3,4-(MeO)2C6H3
S
Tol
S
S
OMe
OMe
O
Ph
H
O
4ah, Tol, 3,4-Cl2C6H3, 3,4-(MeO)2C6H3
OH
Ph
2a (84%)
Ph
OH
OMe
OMe
aThe reactions were performed using a 0.3 mmol scale with 4,
OMe
OMe
H
A-15
C
7a
NaBH4 (38 mg, 1.0 mmol), THF/MeOH (v/v = 1/1, 10 mL), 30
o
Considering these results, 4 was reacted via this approach to
afford diversified 2, as shown in Table 3. In addition to 2i (Ar
= 3,4-Cl2C6H3), 2l (Ar = 3-NO2C6H4), 2q (Ar = 3-pyridyl), 2w
min, 25 C; then A-15 (0.1 g), toluene (10 mL), reflux, 10 h.
c
bIsolated yields. 7i (96%), 7l (96%), 7q (96%), 7w (98%), 7x
(94%) were isolated.
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For the annulation of 4g with a naphthyl group, angular 2g
(Scheme 8). Desulfonylation of 2ah with sodium amalgam (6%
was obtained as the only product, and another linear regioi-
somer could be observed. In particular, 2h, having a 4-
chlorophenyl group, was isolated in an 83% yield; however, 2i
with a 3,4-dichlorophenyl group could not be produced under
A-15 mediated annulation (entries 8-9). It was considered that
the 3-chloro group controlled the reaction. For the electronic
nature of aryl substituents (Ar’ and Ar) of 4, stronger electron-
withdrawing nitro and trifluoromethyl groups (for 4l, 4w, 4x)
were inappropriate. In the comparison of heterocyclic (3-
pyridyl and 2-thienyl) groups (entries 17-18), 2q with a pyridyl
group was not isolated because the nitrogen atom trapped the
proton such that intramolecular annulation was easily inhibited.
According to the above results, two adjacent stereochemical
centres on skeleton 2 were assigned as the trans orientation.
The structures of 2e, 2g, 2k, 2r and 7l were determined by
single-crystal X-ray analysis.40
Na/Hg) in MeOH followed by benzylic oxidation of the corre-
sponding product with PDC in DMF furnished the indatraline
intermediate 8 in a 64% yield in two steps. Furthermore, syn-
thesis of sulfonyl arylquinoline skeleton 9 was accomplished
with a 75% yield via SnCl2-mediated reduction of 4ai in
CH2Cl2 at 25 °C for 10 h.43 After NaBH4-mediated reduction of
4k, the resulting 1,5-bromoalcohol underwent an intramolecu-
lar CuI-catalysed Ullman coupling rection,44 producing tosyl
chroman 10 in a 48% yield in two steps.45 Then, by the use of
the abovementioned two-step route (desulfonylation and ben-
zylic oxidation), flavanone 11 was prepared in a 52% yield.46
As an extension of the synthetic application of 1v, the isoqui-
noline skeleton was synthesized.47 By using a OsO4/NaIO4-
mediated double bond oxidative cleavage procedure,48 the
cyclopentene moiety of 1v could be converted into a 1,5-
dicarbonyl group. Following, by the inclusion of NH4OAc (a
nitrogen source), 12 was obtained in a 27% yield via the
(5C+1N) annulation process.
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Subsequently, the construction of 2ai-2ak was furnished via
the NaBH4-mediated stereochemical 1,2-reduction of 3v-3w
and 3ad, which was followed by A-15-mediated intramolecular
ring-closure of the corresponding -hydroxysulfones (Scheme
7). For 2ai-2ak, the isolated yields (75%, 70%, 62%, respec-
tively) were lower than the other 2 (in Table 3) due to the steric
hindrance of the R’ group that resulted. The stereochemical
structure of 2ai with three contiguous trans-trans chiral centres
was determined by single-crystal X-ray analysis.40 From the X-
ray structure of 2ai, we also indirectly determined that the rela-
tive stereochemistry of skeleton 3 between the R’ and tosyl
substituents was in the trans-conformation.
Scheme 9. Gram-Scale Synthesis of 8
O
O
Tol
Tol
S
S
O
O
O
Amberlyst 15
toluene
+
O
O
Cl
Cl
Cl
5p (3.42 g, 10 mmol) 6f (1.12 g, 11 mmol)
Cl
4ah (85%, 3.66 g)
O
O
Tol
S
NaBH , THF / MeOH, then
4
1) 6% Na/Hg, MeOH
2) PDC, DMF
O
Amberlyst 15, toluene
Cl
Cl
Cl
Cl
8 (59%, 995 mg)
Scheme 7. Synthesis of 2ai-2ak
R'
2ah (72%, 2.55 g)
O
Tol
R'
O
Tol
S
S
OMe
OMe
1) NaBH , THF / MeOH
4
Because of the potential application of this protocol in syn-
thesis of indatraline intermediate 8, attempts to scale up the
transformation would improve the significance of the results.
Thus, the development of a gram-scale method was highly in
demand. When the scale for the A-15 mediated Knoevenagel
condensation of 5p and 6f increased to 10 mmol (3.42 g) and
11 mmol (1.12 g), 4ah was isolated in an 85% (3.66 g) yield in
toluene at reflux. After NaBH4-mediated reduction and A-15-
promoted intramolecular annulation, 2ah was isolated in a 72%
yield (2.55 g). Finally, the Na/Hg-mediated desulfonylation of
2ah and PDC-mediated benzylic oxidation of the resulting
indane furnished 8 in a 59% yield (995 mg). For the gram scale
(10 mmol) synthesis of 8, the total yield was 36%.
O
O
2) Amberlyst 15, toluene
Ar'
OMe
OMe
Ar'
O
3w, R' = cC H , Ar' = 2-naphthyl
6 4
2ai (75%, X-Ray)
2aj (70%)
2ak (62%)
6
11
3v, R' = cC H , Ar' = 4-PhC H
6 11
3ad, R' = 4-FC H , Ar' = Ph
6
4
Scheme 8. Synthesis of 8-12
O
O
NHMe
Tol
S
1) 6% Na/Hg, MeOH
O
2) PDC, DMF
(64% of two steps)
2ah
8
indatraline
Cl
Cl
Cl
Cl
S
Cl
S
Cl
O
O
O
O
Tol
Tol
Tol
Tol
SnCl , CH Cl
2
2
2
O
O
Ph
O
Ph
N
NO
2
In summary, we have developed an Amberlyst 15 (A-15)
mediated synthetic route for constructing sulfonyl arylindenes
1 and indanes 2 in good to excellent yields, including (1) Kno-
evenagel condensation of 5 and 6, (ii) regio- and/or stereocon-
trolled addition or reduction of 4 and (iii) intramolecular
Friedel-Crafts annulation of the resulting -ketosulfones or -
hydroxysulfones. DFT calculations for the regioselectivity of
the addition reaction have been discussed. The process pro-
vides a facile route for the formation of two carbon-carbon (C-
C) bonds. The use of different sulfonic acids was studied for a
novel and efficient transformation. We took the initiative to
explore the synthetic applications of the developed method
towards the skeletons of indanone, quinoline, chroman, fla-
vanone and isoquinoline. Further investigations regarding the
synthetic researches of β-ketosulfones are underway in our
laboratory.
4ai
9 (75%)
S
S
1) NaBH , THF / MeOH
4
1) 6% Na/Hg, MeOH
O
O
Ph
O
2) CuI, KI, K PO ,
4
toluene, 1,10-Phen
(48% of two steps)
Ph
O
2) PDC, DMF
(52% of two steps)
3
Br
4k
10
O
O
Tol
1) OsO , NMO
4
OMe
S
O
THF / H O, then NaIO
2
4
N
OMe
Ph
O
Ph
OMe
2) NH OAc, MeOH
4
Ph
12
(27% of two steps)
1v
OMe
11
Indatraline (Lu 19-005) is a non-selective monoamine trans-
porter inhibitor that has been shown to block the reuptake of
dopamine, norepinephrine and serotonin with effects similar to
those of cocaine. Many facile and efficient synthetic methods
have been developed.42 Based on the Amberlyst 15-catalysed
route, the formal synthesis of indatraline was investigated
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Experimental Section
7.50 (m, 1H), 7.39-7.35 (m, 2H), 7.30 (d, J = 8.4 Hz, 2H), 6.87
2
(dd, J = 1.6, 8.0 Hz, 1H), 6.66 (s, 1H), 6.65 (d, J = 9.6 Hz, 1H),
5.86 (s, 2H), 2.41 (s, 3H); 13C{1H} NMR (100 MHz, CDCl3): δ
192.5, 150.1, 148.1, 144.6, 140.7, 137.5, 136.9, 135.6, 134.4,
129.80 (2x), 129.75 (2x), 128.8 (2x), 128.5 (2x), 126.7, 125.5,
109.1, 108.6, 101.7, 21.6.
3
4
5
6
7
8
9
General. All reagents and solvents were commercial grade
and were used without further purification. All reactions were
routinely performed under an air atmosphere with magnetic
stirring (an open-vessel condition). All products in organic
solvents were dried with anhydrous MgSO4 before concentra-
tion in vacuo under reduced pressure. Melting points (mp) were
3-(3-Methoxyphenyl)-1-phenyl-2-(toluene-4-
1
measured with a SMP3 melting apparatus. H (400 MHz) and
sulfonyl)propenone (4c). 4c was synthesized according to gen-
eral synthetic procedure from 5a (137 mg, 0.5 mmol) and 6c
(82 mg, 0.6 mmol). Yield = 96% (188 mg); Colorless solid; mp
= 115-117 oC (recrystallized from hexanes and EtOAc); HRMS
(ESI-TOF) m/z: [M + H]+ Calcd for C23H21O4S 393.1161;
13C NMR (100 MHz) spectra were recorded on a Varian
INOVA-400 spectrometer, respectively. Chemical shifts (δ) are
reported in ppm and the J values are given in Hertz. High-
resolution mass spectra (HRMS) were measured with a double
focusing mass spectrometer by ESI using a hybrid ion-trap. X-
ray crystal structures were determined with a diffractometer
(CAD4, Kappa CCD).
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
1
Found 393.1163; H NMR (400 MHz, CDCl3): δ 8.00 (s, 1H),
7.92-7.89 (m, 2H), 7.78 (d, J = 8.4 Hz, 2H), 7.53-7.49 (m, 1H),
7.38-7.33 (m, 2H), 7.32 (d, J = 8.0 Hz, 2H), 7.11 (t, J = 8.0 Hz,
1H), 6.89 (d, J = 7.6 Hz, 1H), 6.80 (ddd, J = 0.8, 2.4, 8.4 Hz,
1H), 6.75 (t, J = 2.4 Hz, 1H), 3.55 (s, 3H), 2.42 (s, 3H); 13C{1H}
NMR (100 MHz, CDCl3): δ 192.2, 159.5, 144.8, 140.9, 139.9,
136.6, 135.5, 134.4, 132.6, 129.8, 129.7 (4x), 128.8 (2x), 128.6
(2x), 123.0, 117.7, 114.2, 55.0, 21.6.
For the starting substrates 5, these compounds were known
1
and their related analytical data (e.g., mp, H NMR, 13C NMR
and HRMS) were consistent with those in the references 34-36.
For the starting substrates 6, these materials were purchased
commercially and were used without further purification.
3-(4-Methoxyphenyl)-1-phenyl-2-(toluene-4-
General synthetic procedure of skeleton 4 is as follows:
Amberlyst® 15 (A-15, 100 mg) was added to a solution of β-
sulfonyl)propenone (4d). 4d was synthesized according to gen-
eral synthetic procedure from 5a (137 mg, 0.5 mmol) and 6d
(82 mg, 0.6 mmol). Yield = 93% (182 mg); Colorless solid; mp
= 131-133 oC (recrystallized from hexanes and EtOAc); HRMS
(ESI-TOF) m/z: [M + H]+ Calcd for C23H21O4S 393.1161;
o
ketosulfones 5 (0.5 mmol) in toluene (20 mL) at 25 C. The
o
reaction mixture was stirred at 25 C for 10 min under Dean-
Stark distillation apparatus. Arylaldehydes 6 (0.6 mmol) was
o
1
added to the reaction mixture at 25 C. The reaction mixture
Found 393.1160; H NMR (400 MHz, CDCl3): δ 7.96 (s, 1H),
was stirred at reflux for 3 h. The reaction mixture was cooled
7.93-7.90 (m, 2H), 7.76 (d, J = 8.0 Hz, 2H), 7.53-7.49 (m, 1H),
7.37-7.33 (m, 2H), 7.30 (d, J = 8.0 Hz, 2H), 7.22 (d, J = 8.8 Hz,
2H), 6.70 (d, J = 8.4 Hz, 2H), 3.71 (s, 3H), 2.41 (s, 3H);
13C{1H} NMR (100 MHz, CDCl3): δ 192.7, 161.8, 144.5, 140.8,
137.1, 136.8, 135.6, 134.3, 132.3 (2x), 129.8 (2x), 129.7 (2x),
128.7 (2x), 128.4 (2x), 123.9, 114.3 (2x), 55.2, 21.6.
o
to 25 C. A-15 was filtered by filter paper and the A-15 was
washed with toluene (3 x 5 mL). The combined toluene layers
were concentrated. The residue was diluted with saturated
NaHCO3(aq) (10 mL) and the mixture was extracted with EtOAc
(3 x 20 mL). The combined organic layers were washed with
brine (2 x 10 mL), dried (MgSO4), filtered and evaporated to
afford crude product mixture under reduced pressure. The re-
maining mixture was separated by column chromatography
(silica gel, hexanes/EtOAc = 8/1~4/1 as eluent) affording 4. A-
15 was dried and recovered for the next reaction cycle of in-
termolecular Knoevenagel condensation.
1-Phenyl-2-(toluene-4-sulfonyl)-3-(3,4,5-
trimethoxyphenyl)propenone (4e). 4e was synthesized accord-
ing to general synthetic procedure from 5a (137 mg, 0.5 mmol)
and 6e (118 mg, 0.6 mmol). Yield = 93% (210 mg); Colorless
liquid; HRMS (ESI-TOF) m/z: [M + H]+ Calcd for C25H25O6S
1
453.1372; Found 453.1373; H NMR (400 MHz, CDCl3): δ
3-(3,4-Dimethoxyphenyl)-1-phenyl-2-(toluene-4-
7.94 (s, 1H), 7.94-7.91 (m, 2H), 7.77 (d, J = 8.4 Hz, 2H), 7.53-
7.49 (m, 1H), 7.38-7.34 (m, 2H), 7.30 (d, J = 8.4 Hz, 2H), 6.48
(s, 2H), 3.74 (s, 3H), 3.56 (s, 6H), 2.39 (s, 3H); 13C{1H} NMR
(100 MHz, CDCl3): δ 192.4, 152.9 (2x), 144.6, 141.0, 140.3,
138.4, 136.7, 135.5, 134.4, 129.6 (2x), 129.5 (2x), 128.8 (2x),
128.4 (2x), 126.4, 107.7 (2x), 60.7, 55.7 (2x), 21.5.
sulfonyl)propenone (4a). 4a was synthesized according to gen-
eral synthetic procedure from 5a (137 mg, 0.5 mmol) and 6a
(100 mg, 0.6 mmol). Yield = 92% (194 mg); Colorless solid;
o
mp = 134-136 C (recrystallized from hexanes and EtOAc);
HRMS (ESI-TOF) m/z: [M + H]+ Calcd for C24H23O5S
1
423.1266; Found 423.1266; H NMR (400 MHz, CDCl3): δ
1,3-Diphenyl-2-(toluene-4-sulfonyl)propenone (4f). 4f was
synthesized according to general synthetic procedure from 5a
(137 mg, 0.5 mmol) and 6f (64 mg, 0.6 mmol). Yield = 94%
(170 mg); Colorless liquid; HRMS (ESI-TOF) m/z: [M + H]+
Calcd for C22H19O3S 363.1055; Found 363.1054; 1H NMR
(400 MHz, CDCl3): δ 8.03 (s, 1H), 7.91-7.88 (m, 2H), 7.77 (d,
J = 8.4 Hz, 2H), 7.54-7.49 (m, 1H), 7.37-7.17 (m, 9H), 2.43 (s,
3H); 13C{1H} NMR (100 MHz, CDCl3): δ 192.3, 144.8, 141.0,
139.9, 136.7, 135.5, 134.4, 131.5, 131.0, 130.2 (2x), 129.9 (2x),
129.8 (2x), 128.9 (2x), 128.8 (2x), 128.7 (2x), 21.7.
7.95 (s, 1H), 7.94-7.92 (m, 2H), 7.77 (d, J = 8.4 Hz, 2H), 7.54-
7.49 (m, 1H), 7.38-7.34 (m, 2H), 7.31 (d, J = 8.4 Hz, 2H), 6.96
(dd, J = 2.0, 8.4 Hz, 1H), 6.71 (d, J = 8.4 Hz, 1H), 6.65 (d, J =
2.0 Hz, 1H), 3.79 (s, 3H), 3.49 (s, 3H), 2.41 (s, 3H); 13C{1H}
NMR (100 MHz, CDCl3): δ 192.7, 151.5, 148.7, 144.5, 141.1,
137.1, 136.7, 135.7, 134.4, 129.7 (2x), 129.6 (2x), 128.8 (2x),
128.4 (2x), 125.5, 124.0, 112.0, 110.8, 55.8, 55.4, 21.6.
3-Benzo[1,3]dioxol-5-yl-1-phenyl-2-(toluene-4-
sulfonyl)propenone (4b). 4b was synthesized according to gen-
eral synthetic procedure from 5a (137 mg, 0.5 mmol) and 6b
(90 mg, 0.6 mmol). Yield = 95% (193 mg); Colorless liquid;
HRMS (ESI-TOF) m/z: [M + H]+ Calcd for C23H19O5S
3-Naphthalen-2-yl-1-phenyl-2-(toluene-4-
sulfonyl)propenone (4g). 4g was synthesized according to gen-
eral synthetic procedure from 5a (137 mg, 0.5 mmol) and 6g
(94 mg, 0.6 mmol). Yield = 90% (185 mg); Colorless solid; mp
1
407.0953; Found 407.0954; H NMR (400 MHz, CDCl3): δ
7.91-7.89 (m, 2H), 7.90 (s, 1H), 7.75 (d, J = 8.0 Hz, 2H), 7.54-
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7
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= 164-166 oC (recrystallized from hexanes and EtOAc); HRMS
(s, 3H); 13C{1H} NMR (100 MHz, CDCl3): δ 191.3, 145.0,
142.3, 140.5, 136.5, 135.5, 134.3, 133.0, 132.3, 131.6, 130.3,
129.8 (2x), 129.6 (2x), 128.9 (2x), 128.6 (2x), 127.4, 124.5,
21.7.
(ESI-TOF) m/z: [M + H]+ Calcd for C26H21O3S 413.1212;
1
Found 413.1213; H NMR (400 MHz, CDCl3): δ 8.22 (s, 1H),
7.96-7.94 (m, 2H), 7.86 (d, J = 0.8 Hz, 1H), 7.83 (d, J = 8.4 Hz,
2H), 7.73-7.68 (m, 2H), 7.59 (d, J = 8.8 Hz, 1H), 7.49-7.44 (m,
3H), 7.35-7.25 (m, 5H), 2.43 (s, 3H); 13C{1H} NMR (100 MHz,
CDCl3): δ 192.5, 144.8, 141.1, 139.7, 136.8, 135.7, 134.4,
134.0, 132.7, 132.0, 129.8 (3x), 128.9, 128.7 (3x), 128.6 (4x),
127.9, 127.6, 126.8, 125.5, 21.6.
3-(3-Nitrophenyl)-1-phenyl-2-(toluene-4-sulfonyl)propenone
(4l). 4l was synthesized according to general synthetic proce-
dure from 5a (137 mg, 0.5 mmol) and 6l (91 mg, 0.6 mmol).
o
Yield = 92% (187 mg); Colorless solid; mp = 160-162 C (re-
9
crystallized from hexanes and EtOAc); HRMS (ESI-TOF) m/z:
[M + H]+ Calcd for C22H18NO5S 408.0906; Found 408.0904;
1H NMR (400 MHz, CDCl3): δ 8.12 (t, J = 1.6 Hz, 1H), 8.06 (s,
1H), 8.05 (dd, J = 1.6, 8.0 Hz, 1H), 7.87-7.85 (m, 2H), 7.76 (d,
J = 8.4 Hz, 2H), 7.56 (d, J = 8.0 Hz, 1H), 7.51-7.47 (m, 1H),
7.38-7.33 (m, 3H), 7.32 (d, J = 8.0 Hz, 2H), 2.41 (s, 3H);
13C{1H} NMR (100 MHz, CDCl3): δ 191.4, 148.0, 145.3, 143.3,
137.7, 135.8, 135.0 (2x), 134.7, 133.0, 129.9, 129.8 (2x), 129.6
(2x), 128.8 (2x), 128.7 (2x), 125.0, 124.4, 21.5.
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3-(4-Chlorophenyl)-1-phenyl-2-(toluene-4-
sulfonyl)propenone (4h). 4h was synthesized according to gen-
eral synthetic procedure from 5a (137 mg, 0.5 mmol) and 6h
(84 mg, 0.6 mmol). Yield = 96% (190 mg); Colorless solid; mp
= 162-164 oC (recrystallized from hexanes and EtOAc); HRMS
(ESI-TOF) m/z: [M + H]+ Calcd for C22H18ClO3S 397.0665;
1
Found 397.0668; H NMR (400 MHz, CDCl3): δ 7.98 (s, 1H),
7.89-7.86 (m, 2H), 7.76 (d, J = 8.0 Hz, 2H), 7.53-7.49 (m, 1H),
7.36 (d, J = 8.0 Hz, 2H), 7.33-7.30 (m, 2H), 7.20 (d, J = 8.8 Hz,
2H), 7.15 (d, J = 8.8 Hz, 2H), 2.40 (s, 3H); 13C{1H} NMR (100
MHz, CDCl3): δ 192.0, 144.9, 140.4, 139.3, 137.0, 136.4,
135.2, 134.5, 131.2 (2x), 129.8, 129.71 (2x), 129.69 (2x), 129.1
(2x), 128.8 (2x), 128.6 (2x), 21.5.
3-(4-Hydroxyphenyl)-1-phenyl-2-(toluene-4-
sulfonyl)propenone (4m). 4m was synthesized according to
general synthetic procedure from 5a (137 mg, 0.5 mmol) and
6m (73 mg, 0.6 mmol). Yield = 94% (178 mg); Colorless solid;
mp = 79-81 oC (recrystallized from hexanes and EtOAc);
HRMS (ESI-TOF) m/z: [M + H]+ Calcd for C22H19O4S
3-(3,4-Dichlorophenyl)-1-phenyl-2-(toluene-4-
1
sulfonyl)propenone (4i). 4i was synthesized according to gen-
eral synthetic procedure from 5a (137 mg, 0.5 mmol) and 6i
(104 mg, 0.6 mmol). Yield = 95% (204 mg); Colorless solid;
379.1004; Found 379.1005; H NMR (400 MHz, CDCl3): δ
9.25 (br s, 1H), 7.86 (s, 1H), 7.79 (d, J = 8.4 Hz, 2H), 7.66 (d, J
= 8.4 Hz, 2H), 7.43-7.39 (m, 1H), 7.27-7.19 (m, 4H), 7.04 (d, J
= 8.8 Hz, 2H), 6.57 (d, J = 8.8 Hz, 2H), 2.31 (s, 3H); 13C{1H}
NMR (100 MHz, CDCl3): δ 192.5, 160.2, 144.2, 141.4, 137.1,
135.4, 135.1, 134.0, 132.4 (2x), 129.5 (2x), 129.4 (2x), 128.5
(2x), 128.0 (2x), 122.2, 115.9 (2x), 21.3.
o
mp = 151-153 C (recrystallized from hexanes and EtOAc);
HRMS (ESI-TOF) m/z: [M + H]+ Calcd for C22H17Cl2O3S
1
431.0276; Found 431.0278; H NMR (400 MHz, CDCl3): δ
7.91 (s, 1H), 7.88-7.86 (m, 2H), 7.75 (d, J = 8.4 Hz, 2H), 7.56-
7.52 (m, 1H), 7.39 (d, J = 8.4 Hz, 2H), 7.36 (d, J = 8.4 Hz, 1H),
7.33 (d, J = 8.4 Hz, 2H), 7.04 (d, J = 8.4 Hz, 1H), 7.06 (dd, J =
2.0, 8.4 Hz, 1H), 2.43 (s, 3H); 13C{1H} NMR (100 MHz,
CDCl3): δ 191.7, 145.2, 142.0, 137.8, 136.1, 135.2, 135.1,
134.8, 133.2, 131.8, 131.4, 130.8, 129.8 (2x), 129.7 (2x), 128.9
(2x), 128.7 (2x), 128.6, 21.7.
3-Biphenyl-4-yl-1-phenyl-2-(toluene-4-sulfonyl)propenone
(4n). 4n was synthesized according to general synthetic proce-
dure from 5a (137 mg, 0.5 mmol) and 6n (109 mg, 0.6 mmol).
o
Yield = 90% (197 mg); Colorless solid; mp = 151-153 C (re-
crystallized from hexanes and EtOAc); HRMS (ESI-TOF) m/z:
1
[M + H]+ Calcd for C28H23O3S 439.1368; Found 439.1369; H
3-(4-Fluorophenyl)-1-phenyl-2-(toluene-4-
NMR (400 MHz, CDCl3): δ 8.07 (s, 1H), 7.96-7.84 (m, 2H),
7.80 (d, J = 8.4 Hz, 2H), 7.55-7.31 (m, 14H), 2.43 (s, 3H);
13C{1H} NMR (100 MHz, CDCl3): δ 192.4, 144.7, 143.6, 140.5,
139.44, 139.37, 136.8, 135.6, 134.4, 130.8 (2x), 130.3, 129.9
(2x), 129.7 (2x), 128.83 (2x), 128.79 (2x), 128.6 (2x), 128.1,
127.3 (2x), 126.9 (2x), 21.6. Single-crystal X-Ray diagram:
crystal of 4n was grown by slow diffusion of EtOAc into a
solution of 4n in CH2Cl2 to yield colorless prisms. The com-
pound crystallizes in the monoclinic crystal system, space
group P 21/n, a = 14.5709(16) Å , b = 8.0748(8) Å , c = 18.602(2)
Å , V = 2188.3(4) Å 3, Z = 4, dcalcd = 1.331 g/cm3, F(000) = 920,
2θ range 1.760 ~26.369o, R indices (all data) R1 = 0.0575,
wR2 = 0.151.
sulfonyl)propenone (4j). 4j was synthesized according to gen-
eral synthetic procedure from 5a (137 mg, 0.5 mmol) and 6j
(74 mg, 0.6 mmol). Yield = 94% (179 mg); Colorless solid; mp
= 134-136 oC (recrystallized from hexanes and EtOAc); HRMS
(ESI-TOF) m/z: [M + H]+ Calcd for C22H18FO3S 381.0961;
1
Found 381.0960; H NMR (400 MHz, CDCl3): δ 8.00 (s, 1H),
7.89-7.87 (m, 2H), 7.77 (d, J = 8.4 Hz, 2H), 7.52-7.48 (m, 1H),
7.35 (d, J = 8.0 Hz, 2H), 7.32-7.25 (m, 4H), 6.89-6.84 (m, 2H),
2.40 (s, 3H); 13C{1H} NMR (100 MHz, CDCl3): δ 192.1, 163.8
(d, J = 251.7 Hz), 144.8, 139.6 (d, J = 1.6 Hz), 139.5, 136.5,
135.3, 134.4, 132.2 (d, J = 9.1 Hz, 2x), 129.7 (4x), 128.7 (2x),
128.5 (2x), 127.6 (d, J = 3.0 Hz), 116.0 (d, J = 22.0 Hz, 2x),
21.5.
1-Phenyl-2-(toluene-4-sulfonyl)-3-p-tolylpropenone (4o). 4o
was synthesized according to general synthetic procedure from
5a (137 mg, 0.5 mmol) and 6o (72 mg, 0.6 mmol). Yield =
3-(2-Bromophenyl)-1-phenyl-2-(toluene-4-
sulfonyl)propenone (4k). 4k was synthesized according to gen-
eral synthetic procedure from 5a (137 mg, 0.5 mmol) and 6k
(110 mg, 0.6 mmol). Yield = 93% (205 mg); Colorless solid;
o
90% (169 mg); Colorless solid; mp = 130-132 C (recrystal-
lized from hexanes and EtOAc); HRMS (ESI-TOF) m/z: [M +
o
1
mp = 124-126 C (recrystallized from hexanes and EtOAc);
H]+ Calcd for C23H21O3S 377.1211; Found 377.1210; H NMR
HRMS (ESI-TOF) m/z: [M + H]+ Calcd for C22H18BrO3S
(400 MHz, CDCl3): δ 8.01 (s, 1H), 7.92-7.90 (m, 2H), 7.78 (d,
J = 8.4 Hz, 2H), 7.52-7.47 (m, 1H), 7.35 (d, J = 8.0 Hz, 2H),
7.33-7.29 (m, 2H), 7.17 (d, J = 8.4 Hz, 2H), 6.99 (d, J = 8.0 Hz,
2H), 2.41 (s, 3H), 2.22 (s, 3H); 13C{1H} NMR (100 MHz,
CDCl3): δ 192.4, 144.5, 141.7, 141.0, 138.4, 136.8, 135.5,
1
441.0160; Found 441.0163; H NMR (400 MHz, CDCl3): δ
8.33 (s, 1H), 7.81 (d, J = 8.4 Hz, 2H), 7.78-7.75 (m, 2H), 7.51-
7.48 (m, 1H), 7.46-7.42 (m, 1H), 7.34 (d, J = 8.4 Hz, 2H),
7.31-7.27 (m, 2H), 7.07-7.03 (m, 2H), 7.01-6.96 (m, 1H), 2.44
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134.2, 130.2 (2x), 129.7 (2x), 129.6 (2x), 129.5 (2x), 128.6
HRMS (ESI-TOF) m/z: [M + H]+ Calcd for C25H25O6S
2
1
(2x), 128.5, 128.5 (2x), 21.5, 21.3.
453.1372; Found 453.1374; H NMR (400 MHz, CDCl3): δ
3
7.91 (d, J = 8.4 Hz, 2H), 7.89 (s, 1H), 7.76 (d, J = 8.4 Hz, 2H),
7.30 (d, J = 8.0 Hz, 2H), 6.98 (dd, J = 2.0, 8.4 Hz, 1H), 6.83 (d,
J = 8.8 Hz, 2H), 6.72 (d, J = 8.8 Hz, 1H), 6.70 (d, J = 2.0 Hz,
1H), 3.80 (s, 6H), 3.51 (s, 3H), 2.40 (s, 3H); 13C{1H} NMR
(100 MHz, CDCl3): δ 190.8, 164.6, 151.4, 148.6, 144.4, 140.5,
137.1, 137.0, 132.2 (2x), 129.6 (2x), 128.9, 128.4 (2x), 125.4,
124.2, 114.1 (2x), 111.9, 110.8, 55.8, 55.44, 55.39, 21.6.
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5
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8
9
3-(2-Allyl-3,4-dimethoxyphenyl)-1-phenyl-2-(toluene-4-
sulfonyl)propenone (4p). 4p was synthesized according to gen-
eral synthetic procedure from 5a (137 mg, 0.5 mmol) and 6p
(124 mg, 0.6 mmol). Yield = 83% (192 mg); Colorless liquid;
HRMS (ESI-TOF) m/z: [M + H]+ Calcd for C27H27O5S
1
463.1579; Found 463.1580; H NMR (400 MHz, CDCl3): δ
8.23 (s, 1H), 7.79-7.76 (m, 4H), 7.47-7.43 (m, 1H), 7.33-7.27
(m, 4H), 6.80 (d, J = 8.8 Hz, 1H), 6.44 (d, J = 8.8 Hz, 1H),
6.01-5.93 (m, 1H), 5.19 (dq, J = 1.6, 10.0 Hz, 1H), 5.05 (dq, J
= 1.6, 17.2 Hz, 1H), 3.74 (s, 3H), 3.73 (s, 3H), 3.64 (d, J = 5.6
Hz, 2H), 2.43 (s, 3H); 13C{1H} NMR (100 MHz, CDCl3): δ
192.7, 154.8, 147.2, 144.5, 139.9, 138.7, 137.3, 136.1, 135.8,
134.0, 129.70 (2x), 129.68 (2x), 128.6 (2x), 128.5 (3x), 126.2,
124.1, 116.4, 110.0, 60.9, 55.5, 30.7, 21.7.
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3-(3,4-Dimethoxyphenyl)-2-(toluene-4-sulfonyl)-1-p-
tolylpropenone (4v). 4v was synthesized according to general
synthetic procedure from 5d (144 mg, 0.5 mmol) and 6a (100
mg, 0.6 mmol). Yield = 95% (207 mg); Colorless liquid;
HRMS (ESI-TOF) m/z: [M + H]+ Calcd for C25H25O5S
1
437.1423; Found 437.1425; H NMR (400 MHz, CDCl3): δ
7.92 (s, 1H), 7.82 (d, J = 8.0 Hz, 2H), 7.76 (d, J = 8.4 Hz, 2H),
7.28 (d, J = 8.4 Hz, 2H), 7.14 (d, J = 8.4 Hz, 2H), 6.96 (dd, J =
2.0, 8.4 Hz, 1H), 6.70 (d, J = 8.4 Hz, 1H), 6.66 (d, J = 2.0 Hz,
1H), 3.76 (s, 3H), 3.48 (s, 3H), 2.38 (s, 3H), 2.31 (s, 3H);
13C{1H} NMR (100 MHz, CDCl3): δ 192.1, 151.3, 148.5, 145.6,
144.3, 140.7, 137.1, 136.8, 133.3, 129.7 (2x), 129.52 (2x),
129.48 (2x), 128.3 (2x), 125.4, 124.0, 111.9, 110.7, 55.7, 55.3,
21.6, 21.5.
1-Phenyl-3-pyridin-3-yl-2-(toluene-4-sulfonyl)propenone
(4q). 4q was synthesized according to general synthetic proce-
dure from 5a (137 mg, 0.5 mmol) and 6q (64 mg, 0.6 mmol).
Yield = 80% (145 mg); Colorless liquid; HRMS (ESI-TOF)
m/z: [M + H]+ Calcd for C21H18NO3S 364.1007; Found
364.1009; 1H NMR (400 MHz, CDCl3): δ 8.55 (s, 1H), 8.43 (d,
J = 4.0 Hz, 1H), 7.99 (s, 1H), 7.86-7.84 (m, 2H), 7.74 (d, J =
8.4 Hz, 2H), 7.51-7.46 (m, 2H), 7.34 (d, J = 7.6 Hz, 2H), 7.30
(d, J = 8.4 Hz, 2H), 7.06 (dd, J = 4.8, 8.0 Hz, 1H), 2.39 (s, 3H);
13C{1H} NMR (100 MHz, CDCl3): δ 191.5, 151.3, 150.9, 145.1,
142.4, 136.9, 136.1, 135.9, 135.0, 134.7, 129.8 (2x), 129.7 (2x),
128.8 (2x), 128.6 (2x), 127.5, 123.4, 21.5.
3-(3,4-Dimethoxyphenyl)-2-(toluene-4-sulfonyl)-1-(4-
trifluoromethylphenyl)propenone (4w). 4w was synthesized
according to general synthetic procedure from 5e (171 mg, 0.5
mmol) and 6a (100 mg, 0.6 mmol). Yield = 92% (225 mg);
Colorless liquid; HRMS (ESI-TOF) m/z: [M + H]+ Calcd for
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C25H22F3O5S 491.1140; Found 491.1143; H NMR (400 MHz,
1-Phenyl-3-thiophen-2-yl-2-(toluene-4-sulfonyl)propenone
(4r). 4r was synthesized according to general synthetic proce-
dure from 5a (137 mg, 0.5 mmol) and 6r (67 mg, 0.6 mmol).
CDCl3): δ 8.02 (d, J = 8.4 Hz, 2H), 8.01 (s, 1H), 7.76 (d, J =
8.4 Hz, 2H), 7.61 (d, J = 8.4 Hz, 2H), 7.30 (d, J = 8.0 Hz, 2H),
6.92 (dd, J = 2.0, 8.4 Hz, 1H), 6.70 (d, J = 8.4 Hz, 1H), 6.65 (d,
J = 2.0 Hz, 1H), 3.77 (s, 3H), 3.55 (s, 3H), 2.39 (s, 3H); 13C{1H}
NMR (100 MHz, CDCl3): δ 192.0, 151.8, 148.8, 144.7, 141.7,
138.2, 136.8, 136.2, 135.2 (q, J = 32.6 Hz), 129.9 (2x), 129.7
(2x), 128.4 (2x), 125.9 (q, J = 271.4 Hz), 125.8 (d, J = 3.8 Hz,
2x), 125.1, 123.6, 112.1, 111.0, 55.7, 55.4, 21.5.
o
Yield = 84% (155 mg); Colorless solid; mp = 142-144 C (re-
crystallized from hexanes and EtOAc); HRMS (ESI-TOF) m/z:
1
[M + H]+ Calcd for C20H17O3S2 369.0619; Found 369.0621; H
NMR (400 MHz, CDCl3): δ 8.08 (s, 1H), 8.01-7.98 (m, 2H),
7.74 (d, J = 8.4 Hz, 2H), 7.59-7.55 (m, 1H), 7.43-7.39 (m, 2H),
7.34 (dd, J = 0.8, 4.8 Hz, 1H), 7.29 (d, J = 8.0 Hz, 2H), 7.22
(dd, J = 0.8, 4.0 Hz, 1H), 6.93 (dd, J = 4.0, 4.8 Hz, 1H), 2.40 (s,
3H); 13C{1H} NMR (100 MHz, CDCl3): δ 191.7, 144.6, 136.7,
136.6, 135.5, 134.6, 134.4, 134.3, 133.0, 132.3, 130.0 (2x),
129.7 (2x), 128.8 (2x), 128.4 (2x), 127.9, 21.6.
3-(3,4-Dimethoxyphenyl)-1-(4-nitrophenyl)-2-(toluene-4-
sulfonyl)propenone (4x). 4x was synthesized according to gen-
eral synthetic procedure from 5f (160 mg, 0.5 mmol) and 6a
(100 mg, 0.6 mmol). Yield = 90% (210 mg); Colorless liquid;
HRMS (ESI-TOF) m/z: [M + H]+ Calcd for C24H22NO7S
3-(3,4-Dimethoxyphenyl)-1-(4-fluorophenyl)-2-(toluene-4-
sulfonyl)propenone (4t). 4t was synthesized according to gen-
eral synthetic procedure from 5b (146 mg, 0.5 mmol) and 6a
(100 mg, 0.6 mmol). Yield = 98% (216 mg); Colorless liquid;
HRMS (ESI-TOF) m/z: [M + H]+ Calcd for C24H22FO5S
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468.1117; Found 468.1118; H NMR (400 MHz, CDCl3): δ
8.20 (d, J = 9.2 Hz, 2H), 8.06 (d, J = 9.2 Hz, 2H), 8.05 (d, J =
0.8 Hz, 1H), 7.77 (d, J = 8.4 Hz, 2H), 7.35 (d, J = 8.4 Hz, 2H),
6.90 (dd, J = 2.4, 8.4 Hz, 1H), 6.70 (d, J = 8.4 Hz, 1H), 6.64 (d,
J = 2.4 Hz, 1H), 3.80 (s, 3H), 3.60 (s, 3H), 2.44 (s, 3H); 13C{1H}
NMR (100 MHz, CDCl3): δ 191.6, 152.0, 150.8, 149.0, 145.0,
142.3, 140.0, 136.8, 136.1, 130.6 (2x), 129.9 (2x), 128.5 (2x),
125.1, 124.0 (2x), 123.6, 112.2, 111.1, 55.9, 55.6, 21.7.
1
441.1172; Found 441.1175; H NMR (400 MHz, CDCl3): δ
7.97-7.94 (m, 2H), 7.94 (s, 1H), 7.76 (d, J = 8.4 Hz, 2H), 7.31
(d, J = 8.0 Hz, 2H), 7.05-7.01 (m, 2H), 6.94 (dd, J = 1.6, 8.0
Hz, 1H), 6.71 (d, J = 8.4 Hz, 1H), 6.65 (d, J = 2.0 Hz, 1H),
3.80 (s, 3H), 3.53 (s, 3H), 2.41 (s, 3H); 13C{1H} NMR (100
MHz, CDCl3): δ 191.1, 166.4 (d, J = 255.4 Hz), 151.6, 148.7,
144.6, 141.2, 137.0, 136.5, 132.5 (d, J = 9.8 Hz, 2x), 132.2 (d,
J = 3.0 Hz), 129.7 (2x), 128.4 (2x), 125.3, 123.9, 116.1 (d, J =
22.0 Hz, 2x), 112.0, 110.9, 55.8, 55.4, 21.6.
1-Biphenyl-4-yl-3-(3,4-dimethoxyphenyl)-2-(toluene-4-
sulfonyl)propenone (4y). 4y was synthesized according to gen-
eral synthetic procedure from 5g (175 mg, 0.5 mmol) and 6a
(100 mg, 0.6 mmol). Yield = 90% (224 mg); Colorless liquid;
HRMS (ESI-TOF) m/z: [M + H]+ Calcd for C30H27O5S
1
499.1579; Found 499.1581; H NMR (400 MHz, CDCl3): δ
3-(3,4-Dimethoxyphenyl)-1-(4-methoxyphenyl)-2-(toluene-4-
sulfonyl)propenone (4u). 4u was synthesized according to gen-
eral synthetic procedure from 5c (152 mg, 0.5 mmol) and 6a
(100 mg, 0.6 mmol). Yield = 97% (219 mg); Colorless liquid;
8.03 (d, J = 8.4 Hz, 2H), 7.99 (s, 1H), 7.81 (d, J = 8.4 Hz, 2H),
7.60 (d, J = 8.4 Hz, 2H), 7.56-7.53 (m, 2H), 7.44-7.34 (m, 3H),
7.32 (d, J = 8.0 Hz, 2H), 7.01 (dd, J = 2.0, 8.4 Hz, 1H), 6.73 (d,
J = 2.0 Hz, 1H), 6.73 (d, J = 8.4 Hz, 1H), 3.78 (s, 3H), 3.54 (s,
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3H), 2.41 (s, 3H); 13C{1H} NMR (100 MHz, CDCl3): δ 192.2,
151.5, 148.7, 147.0, 144.5, 140.9, 139.3, 137.1, 136.8, 134.4,
130.3 (2x), 129.6 (2x), 128.8 (2x), 128.4 (3x), 127.4 (2x),
127.1 (2x), 125.4, 124.0, 112.0, 110.8, 55.7, 55.4, 21.5.
3-(3,4-Dimethoxyphenyl)-2-(4-ethylbenzenesulfonyl)-1-
phenylpropenone (4ad). 4ad was synthesized according to gen-
eral synthetic procedure from 5l (144 mg, 0.5 mmol) and 6a
(100 mg, 0.6 mmol). Yield = 94% (205 mg); Colorless solid;
o
mp = 110-112 C (recrystallized from hexanes and EtOAc);
3-(3,4-Dimethoxyphenyl)-1-naphthalen-2-yl-2-(toluene-4-
sulfonyl)propenone (4z). 4z was synthesized according to gen-
eral synthetic procedure from 5h (162 mg, 0.5 mmol) and 6a
(100 mg, 0.6 mmol). Yield = 92% (217 mg); Colorless liquid;
HRMS (ESI-TOF) m/z: [M + H]+ Calcd for C28H25O5S
HRMS (ESI-TOF) m/z: [M + H]+ Calcd for C25H25O5S
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437.1423; Found 437.1425; H NMR (400 MHz, CDCl3): δ
7.95 (s, 1H), 7.93-7.91 (m, 2H), 7.79 (d, J = 8.8 Hz, 2H), 7.52-
7.48 (m, 1H), 7.37-7.30 (m, 4H), 6.96 (dd, J = 2.0, 8.4 Hz, 1H),
6.70 (d, J = 8.4 Hz, 1H), 6.65 (d, J = 2.0 Hz, 1H), 3.77 (s, 3H),
3.47 (s, 3H), 2.69 (q, J = 7.6 Hz, 2H), 1.22 (t, J = 7.6 Hz, 3H);
13C{1H} NMR (100 MHz, CDCl3): δ 192.6, 151.5, 150.5, 148.6,
141.1, 137.3, 136.7, 135.6, 134.4, 129.6 (2x), 128.8 (2x), 128.5
(2x), 128.4 (2x), 125.5, 124.0, 112.0, 110.8, 55.7, 55.3, 28.7,
14.9.
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473.1423; Found 473.1425; H NMR (400 MHz, CDCl3): δ
8.40 (d, J = 1.6 Hz, 1H), 8.04 (s, 1H), 8.02 (d, J = 1.6 Hz, 1H),
7.83-7.78 (m, 5H), 7.55 (dt, J = 1.2, 8.0 Hz, 1H), 7.46 (dt, J =
1.2, 8.0 Hz, 1H), 7.29 (d, J = 8.0 Hz, 2H), 7.01 (dd, J = 2.0, 8.4
Hz, 1H), 6.73 (d, J = 2.0 Hz, 1H), 6.66 (d, J = 8.4 Hz, 1H),
3.72 (s, 3H), 3.47 (s, 3H), 2.36 (s, 3H); 13C{1H} NMR (100
MHz, CDCl3): δ 192.5, 151.4, 148.6, 144.5, 141.2, 137.0,
136.9, 136.0, 133.1 (2x), 132.3, 129.8, 129.6 (2x), 129.1, 128.8,
128.4 (2x), 127.6, 126.8, 125.4, 124.0, 123.6, 111.9, 110.8,
55.6, 55.3, 21.5.
2-(4-t-Butylbenzenesulfonyl)-3-(3,4-dimethoxyphenyl)-1-
phenylpropenone (4ae). 4ae was synthesized according to gen-
eral synthetic procedure from 5m (158 mg, 0.5 mmol) and 6a
(100 mg, 0.6 mmol). Yield = 93% (216 mg); Colorless liquid;
HRMS (ESI-TOF) m/z: [M + H]+ Calcd for C27H29O5S
2-Benzenesulfonyl-3-(3,4-dimethoxyphenyl)-1-
1
465.1736; Found 465.1735; H NMR (400 MHz, CDCl3): δ
phenylpropenone (4aa). 4aa was synthesized according to gen-
eral synthetic procedure from 5i (130 mg, 0.5 mmol) and 6a
(100 mg, 0.6 mmol). Yield = 90% (184 mg); Colorless solid;
7.94 (s, 1H), 7.92-7.90 (m, 2H), 7.81 (d, J = 8.8 Hz, 2H), 7.52-
7.48 (m, 3H), 7.36-7.32 (m, 2H), 6.97 (dd, J = 2.0, 8.4 Hz, 1H),
6.71 (d, J = 8.4 Hz, 1H), 6.66 (d, J = 2.0 Hz, 1H), 3.78 (s, 3H),
3.48 (s, 3H), 1.31 (s, 9H); 13C{1H} NMR (100 MHz, CDCl3): δ
192.8, 152.3, 151.5, 148.7, 141.1, 137.1, 136.7, 135.7, 134.4,
129.7 (2x), 128.8 (2x), 128.2 (2x), 126.0 (2x), 125.6, 124.0,
112.0, 110.8, 55.8, 55.4, 35.1, 30.9 (3x).
o
mp = 194-196 C (recrystallized from hexanes and EtOAc);
HRMS (ESI-TOF) m/z: [M + H]+ Calcd for C23H21O5S
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409.1110; Found 409.1111; H NMR (400 MHz, CDCl3): δ
7.98 (s, 1H), 7.95-7.89 (m, 4H), 7.63-7.59 (m, 1H), 7.55-7.50
(m, 3H), 7.39-7.35 (m, 2H), 6.98 (dd, J = 2.4, 8.4 Hz, 1H), 6.72
(d, J = 8.4 Hz, 1H), 6.65 (d, J = 2.0 Hz, 1H), 3.80 (s, 3H), 3.49
(s, 3H); 13C{1H} NMR (100 MHz, CDCl3): δ 192.6, 151.6,
148.8, 141.6, 140.2, 136.4, 135.7, 134.5, 133.5, 129.7 (2x),
129.0 (2x), 128.9 (2x), 128.4 (2x), 125.7, 124.0, 112.1, 110.9,
55.8, 55.4.
3-(3,4-Dimethoxyphenyl)-2-methanesulfonyl-1-
phenylpropenone (4af). 4af was synthesized according to gen-
eral synthetic procedure from 5n (99 mg, 0.5 mmol) and 6a
(100 mg, 0.6 mmol). Yield = 96% (166 mg); Colorless solid;
o
mp = 98-100 C (recrystallized from hexanes and EtOAc);
HRMS (ESI-TOF) m/z: [M + H]+ Calcd for C18H19O5S
3-(3,4-Dimethoxyphenyl)-2-(4-fluorobenzenesulfonyl)-1-
phenylpropenone (4ab). 4ab was synthesized according to gen-
eral synthetic procedure from 5j (139 mg, 0.5 mmol) and 6a
(100 mg, 0.6 mmol). Yield = 96% (204 mg); Colorless solid;
1
347.0953; Found 347.0955; H NMR (400 MHz, CDCl3): δ
7.96-7.93 (m, 2H), 7.82 (s, 1H), 7.53-7.48 (m, 1H), 7.37-7.34
(m, 2H), 6.94 (dd, J = 2.4, 8.4 Hz, 1H), 6.70 (d, J = 8.4 Hz,
1H), 6.64 (d, J = 2.4 Hz, 1H), 3.77 (s, 3H), 3.49 (s, 3H), 3.21 (s,
3H); 13C{1H} NMR (100 MHz, CDCl3): δ 193.4, 151.6, 148.6,
142.1, 135.4, 135.2, 134.6, 129.7 (2x), 128.9 (2x), 125.7, 123.5,
112.1, 110.8, 55.7, 55.4, 43.4.
o
mp = 184-186 C (recrystallized from hexanes and EtOAc);
HRMS (ESI-TOF) m/z: [M + H]+ Calcd for C23H20FO5S
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427.1016; Found 427.1015; H NMR (400 MHz, CDCl3): δ
7.96 (s, 1H), 7.93-7.88 (m, 4H), 7.54-7.49 (m, 1H), 7.38-7.34
(m, 2H), 7.20-7.15 (m, 2H), 6.96 (dd, J = 2.0, 8.4 Hz, 1H), 6.71
(d, J = 8.4 Hz, 1H), 6.64 (d, J = 2.0 Hz, 1H), 3.78 (s, 3H), 3.48
(s, 3H); 13C{1H} NMR (100 MHz, CDCl3): δ 192.6, 165.6 (d, J
= 254.7 Hz), 151.7, 148.7, 141.7, 136.2, 136.0, 135.5, 134.5,
131.2 (d, J = 9.9 Hz, 2x), 129.6 (2x), 128.9 (2x), 125.7, 123.8,
116.2 (d, J = 22.8 Hz, 2x), 112.0, 110.8, 55.7, 55.3.
2-(n-Butane-1-sulfonyl)-3-(3,4-dimethoxy-phenyl)-1-phenyl-
propenone (4ag). 4ag was synthesized according to general
synthetic procedure from 5o (120 mg, 0.5 mmol) and 6a (100
mg, 0.6 mmol). Yield = 96% (186 mg); Colorless liquid;
HRMS (ESI-TOF) m/z: [M + H]+ Calcd for C21H25O5S
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389.1423; Found 389.1425; H NMR (400 MHz, CDCl3): δ
7.96-7.93 (m, 2H), 7.74 (s, 1H), 7.51-7.47 (m, 1H), 7.36-7.32
(m, 2H), 6.94 (dd, J = 2.4, 8.4 Hz, 1H), 6.70 (d, J = 8.4 Hz,
1H), 6.65 (d, J = 2.4 Hz, 1H), 3.76 (s, 3H), 3.48 (s, 3H), 3.22-
3.28 (m, 2H), 1.85-1.77 (m, 2H), 1.51-1.41 (m, 2H), 0.92 (t, J
= 7.6 Hz, 3H); 13C{1H} NMR (100 MHz, CDCl3): δ 193.5,
151.5, 148.6, 142.7, 135.4, 134.5, 133.8, 129.7 (2x), 128.8 (2x),
125.6, 123.6, 112.1, 110.8, 55.7, 55.3, 54.4, 24.3, 21.3, 13.4.
3-(3,4-Dimethoxyphenyl)-2-(4-methoxybenzenesulfonyl)-1-
phenylpropenone (4ac). 4ac was synthesized according to gen-
eral synthetic procedure from 5k (145 mg, 0.5 mmol) and 6a
(100 mg, 0.6 mmol). Yield = 96% (210 mg); Colorless liquid;
HRMS (ESI-TOF) m/z: [M + H]+ Calcd for C24H23O6S
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439.1215; Found 439.1216; H NMR (400 MHz, CDCl3): δ
7.94-7.91 (m, 2H), 7.93 (s, 1H), 7.80 (d, J = 8.8 Hz, 2H), 7.52-
7.48 (m, 1H), 7.37-7.33 (m, 2H), 6.96 (d, J = 8.8 Hz, 2H), 6.94
(dd, J = 2.0, 8.4 Hz, 1H), 6.70 (d, J = 8.4 Hz, 1H), 6.64 (d, J =
2.0 Hz, 1H), 3.82 (s, 3H), 3.77 (s, 3H), 3.48 (s, 3H); 13C{1H}
NMR (100 MHz, CDCl3): δ 192.8, 163.6, 151.4, 148.6, 140.5,
137.0, 135.7, 134.4, 131.5, 130.6 (2x), 129.6 (2x), 128.8 (2x),
125.4, 124.0, 114.2 (2x), 111.9, 110.8, 55.7, 55.5, 55.3.
1-(3,4-Dichlorophenyl)-3-phenyl-2-(toluene-4-
sulfonyl)propenone (4ah). 4ah was synthesized according to
general synthetic procedure from 5p (171 mg, 0.5 mmol) and
6f (64 mg, 0.6 mmol). Yield = 96% (206 mg); Colorless solid;
o
mp = 149-151 C (recrystallized from hexanes and EtOAc);
HRMS (ESI-TOF) m/z: [M + H]+ Calcd for C22H17Cl2O3S
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431.0276; Found 431.0277; H NMR (400 MHz, CDCl3): δ
8.06 (s, 1H), 7.93 (dd, J = 0.4, 2.4 Hz, 1H), 7.75 (d, J = 8.4 Hz,
2H), 7.69 (dd, J = 2.4, 8.4 Hz, 1H), 7.43 (dd, J = 0.4, 8.4 Hz,
1H), 7.35-7.28 (m, 3H), 7.25-7.22 (m, 4H), 2.44 (s, 3H);
13C{1H} NMR (100 MHz, CDCl3): δ 190.3, 145.1, 141.6, 139.2,
139.1, 136.3, 135.1, 133.6, 131.4, 131.2, 131.12, 130.95, 130.1
(2x), 129.9 (2x), 129.1 (2x), 128.9, 128.6 (2x), 21.7.
149.4, 144.9, 143.5, 138.5, 136.9, 136.7, 136.1, 133.0, 129.7
(2x), 128.9 (2x), 128.8 (2x), 128.3 (2x), 126.3, 124.4, 21.6.
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3-Furan-2-yl-1-phenyl-2-(toluene-4-sulfonyl)propenone
(4am). 4am was synthesized according to general synthetic
procedure from 5a (137 mg, 0.5 mmol) and 6w (58 mg, 0.6
mmol). Yield = 64% (225 mg); Colorless solid; mp = 170-172
oC (recrystallized from hexanes and EtOAc); HRMS (ESI-TOF)
m/z: [M + H]+ calcd for C20H17O4S 353.0848, found 353.0856;
1H NMR (400 MHz, CDCl3): δ 7.93-7.91 (m, 2H), 7.73 (d, J =
8.4 Hz, 2H), 7.72 (s, 1H), 7.56-7.52 (m, 1H), 7.42-7.37 (m, 2H),
7.29 (d, J = 8.0 Hz, 2H), 7.18 (d, J = 2.0 Hz, 1H), 6.68 (d, J =
3.6 Hz, 1H), 6.33 (dd, J = 2.0, 3.6 Hz, 1H), 2.40 (s, 3H);
13C{1H} NMR (100 MHz, CDCl3): δ 191.1, 147.5, 146.6, 144.6,
136.7, 136.3, 135.7, 133.9, 129.7 (2x), 129.6 (2x), 128.5 (2x),
128.4 (2x), 126.7, 118.9, 112.6, 21.6.
3-(2-Nitrophenyl)-1-phenyl-2-(toluene-4-sulfonyl)propenone
(4ai). 4ai was synthesized according to general synthetic pro-
cedure from 5a (137 mg, 0.5 mmol) and 6t (91 mg, 0.6 mmol).
Yield = 72% (147 mg); Colorless liquid; HRMS (ESI-TOF)
m/z: [M + H]+ Calcd for C22H18NO5S 408.0906; Found
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408.0904; H NMR (400 MHz, CDCl3): δ 8.43 (s, 1H), 8.02
(dd, J = 2.4, 7.2 Hz, 1H), 7.81 (d, J = 8.0 Hz, 2H), 7.64-7.62
(m, 2H), 7.42-7.35 (m, 3H), 7.32 (d, J = 8.0 Hz, 2H), 7.22-7.16
(m, 3H), 2.42 (s, 3H); 13C{1H} NMR (100 MHz, CDCl3): δ
190.4, 146.7, 145.2, 142.6, 138.9, 136.1, 135.8, 134.2, 133.9,
131.0, 130.7, 129.9 (2x), 129.2 (2x), 128.8 (2x), 128.52, 128.49
(2x), 125.0, 21.6.
3-Benzofuran-2-yl-1-phenyl-2-(toluene-4-
sulfonyl)propenone (4an). 4an was synthesized according to
general synthetic procedure from 5a (137 mg, 0.5 mmol) and
6x (88 mg, 0.6 mmol). Yield = 84% (338 mg); Colorless solid;
o
3-(1-Benzyl-1H-pyrrol-2-yl)-1-phenyl-2-(toluene-4-
mp = 168-170 C (recrystallized from hexanes and EtOAc);
sulfonyl)propenone (4aj). 4aj was synthesized according to
general synthetic procedure from 5a (137 mg, 0.5 mmol) and
6u (111 mg, 0.6 mmol). Yield = 80% (353 mg); Colorless
solid; mp = 138-140 oC (recrystallized from hexanes and
EtOAc); HRMS (ESI-TOF) m/z: [M + H]+ calcd for
HRMS (ESI-TOF) m/z: [M + H]+ calcd for C24H19O4S
403.1004, found 403.1009; H NMR (400 MHz, CDCl3): δ
1
8.00-7.97 (m, 2H), 7.85 (s, 1H), 7.79 (d, J = 8.4 Hz, 2H), 7.55-
7.50 (m, 2H), 7.43-7.39 (m, 2H), 7.33 (d, J = 8.4 Hz, 2H), 7.22
(dt, J = 1.2, 8.0 Hz, 1H), 7.15 (dt, J = 1.2, 8.4 Hz, 1H), 7.05 (d,
J = 0.4 Hz, 1H), 7.01 (dd, J = 0.4, 8.0 Hz, 1H), 2.43 (s, 3H);
13C{1H} NMR (100 MHz, CDCl3): δ 190.9, 156.0, 148.8, 144.9,
138.9, 136.7, 136.5, 134.0, 129.8 (2x), 129.5 (2x), 128.7 (2x),
128.6 (2x), 127.5, 127.3, 127.1, 123.6, 122.1, 114.9, 111.4,
21.7.
1
C27H24NO3S 442.1477, found 442.1483; H NMR (400 MHz,
CDCl3): δ 7.86 (s, 1H), 7.79-7.75 (m, 2H), 7.54 (d, J = 8.4 Hz,
2H), 7.53-7.47 (m, 1H), 7.45-7.38 (m, 3H), 7.32-7.28 (m, 2H),
7.20 (d, J = 8.0 Hz, 2H), 7.10-7.08 (m, 2H), 6.89 (dd, J = 1.6,
2.8 Hz, 1H), 6.12 (dd, J = 1.6, 4.4 Hz, 1H), 5.99 (dd, J = 2.8,
4.4 Hz, 1H), 5.25 (s, 2H), 2.37 (s, 3H); 13C{1H} NMR (100
MHz, CDCl3): δ 192.2, 143.9, 137.5, 137.0, 135.3, 133.9,
131.8, 129.5 (2x), 129.4 (2x), 128.9, 128.8 (2x), 128.5 (2x),
128.1, 127.9 (2x), 127.8, 126.4 (2x), 124.3, 117.5, 110.5, 51.1,
21.4.
3-Benzo[b]thiophen-2-yl-1-phenyl-2-(toluene-4-
sulfonyl)propenone (4ao). 4ao was synthesized according to
general synthetic procedure from 5a (137 mg, 0.5 mmol) and
6y (97 mg, 0.6 mmol). Yield = 78% (326 mg); Colorless solid;
o
mp = 183-185 C (recrystallized from hexanes and EtOAc);
2-Benzenesulfonyl-1-phenyl-3-thiophen-2-ylpropenone (4ak).
4ak was synthesized according to general synthetic procedure
from 5i (130 mg, 0.5 mmol) and 6r (67 mg, 0.6 mmol). Yield =
HRMS (ESI-TOF) m/z: [M + H]+ calcd for C24H19O3S2
1
419.0776, found 419.0778; H NMR (400 MHz, CDCl3): δ
8.17 (d, J = 0.8 Hz, 1H), 8.04-8.02 (m, 2H), 7.76 (d, J = 8.4 Hz,
2H), 7.74-7.71 (m, 1H), 7.61-7.57 (m, 2H), 7.54 (s, 1H), 7.46-
7.42 (m, 2H), 7.33-7.28 (m, 4H), 2.42 (s, 3H); 13C{1H} NMR
(100 MHz, CDCl3): δ 191.4, 144.9, 142.3, 139.0, 138.4, 136.5,
135.9, 134.7, 134.5, 133.6, 132.1, 130.2 (2x), 129.8 (2x), 128.9
(2x), 128.6 (2x), 126.7, 125.0, 124.8, 122.3, 21.7.
84% (297 mg); Colorless solid; mp
=
124-126 oC
(recrystallized from hexanes and EtOAc); HRMS (ESI-TOF)
m/z: [M + H]+ calcd for C19H15O3S2 355.0463, found 355.0469;
1H NMR (400 MHz, CDCl3): δ 8.10 (s, 1H), 8.00-7.97 (m, 2H),
7.88-7.85 (m, 2H), 7.63-7.56 (m, 2H), 7.53-7.48 (m, 2H), 7.44-
7.40 (m, 2H), 7.36 (ddd, J = 0.8, 1.6, 4.8 Hz, 1H), 7.22 (ddd, J
= 0.8, 1.6, 3.6 Hz, 1H), 6.95 (dd, J = 3.6, 4.8 Hz, 1H); 13C{1H}
NMR (100 MHz, CDCl3): δ 191.6, 139.8, 136.2, 135.5, 134.7,
134.6, 134.4, 133.6, 133.5, 132.5, 130.0 (2x), 129.1 (2x), 128.9
(2x), 128.4 (2x), 128.0.
General synthetic procedure of skeleton 3 is as follows: Gri-
gnard reagent (R’MgBr, 2 mL, 1.0 M in THF, 2.0 mmol) was
added to a solution of 4 (1.0 mmol) in THF (10 mL) at 25 C.
The reaction mixture was stirred at reflux for 10 h. The reac-
tion mixture was cooled to 25 C and the solvent was concen-
o
o
1-Phenyl-3-pyridin-2-yl-2-(toluene-4-sulfonyl)propenone
(4al). 4al was synthesized according to general synthetic pro-
cedure from 5a (137 mg, 0.5 mmol) and 6v (64 mg, 0.6 mmol).
trated. The residue was diluted with water (10 mL) and the
mixture was extracted with CH2Cl2 (3 x 20 mL). The combined
organic layers were washed with brine (2 x 10 mL), dried
(MgSO4), filtered and evaporated to afford crude product mix-
ture under reduced pressure. The remaining mixture was sepa-
rated by column chromatography (silica gel, hexanes/EtOAc =
8/1~4/1 as eluent) affording 3.
o
Yield = 68% (247 mg); Colorless solid; mp = 221-223 C
(recrystallized from hexanes and EtOAc); HRMS (ESI-TOF)
m/z: [M + H]+ calcd for C21H18NO3S 364.1007, found 364.1015;
1H NMR (400 MHz, CDCl3): δ 8.17 (d, J = 4.0 Hz, 1H), 7.92 (s,
1H), 7.88-7.86 (m, 2H), 7.77 (d, J = 8.4 Hz, 2H), 7.63 (dt, J =
2.0, 7.6 Hz, 1H), 7.48-7.42 (m, 2H), 7.34 (d, J = 8.0 Hz, 2H),
7.30 (d, J = 8.4 Hz, 2H), 7.06 (ddd, J = 0.8, 4.4, 7.6 Hz, 1H),
2.40 (s, 3H); 13C{1H} NMR (100 MHz, CDCl3): δ 190.8, 150.0,
3-Cyclohexyl-1,3-diphenyl-2-(toluene-4-sulfonyl)propan-1-
one (3a). 3a was synthesized according to general synthetic
procedure from 4f (362 mg, 1.0 mmol) and cC6H11MgBr (2 mL,
1.0 M in THF, 2.0 mmol). Yield = 86% (384 mg); Colorless
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2
3
4
5
6
7
8
solid; mp = 184-187 oC (recrystallized from hexanes and
145.2, 137.5, 135.0, 133.2, 132.6 (d, J = 3.1 Hz), 131.1 (2x),
EtOAc); HRMS (ESI-TOF) m/z: [M + H]+ calcd for C28H31O3S
129.8 (2x), 129.4 (2x), 128.3 (2x), 128.2 (2x), 114.5 (d, J =
20.5 Hz, 2x), 70.7, 50.5, 38.4, 32.2, 27.3, 26.6, 26.23, 26.20,
21.6.
1
447.1994, found 447.1996; H NMR (400 MHz, CDCl3): δ
7.71 (d, J = 8.0 Hz, 2H), 7.58-7.54 (m, 2H), 7.44-7.40 (m, 1H),
7.28-7.20 (m, 4H), 7.00-6.95 (m, 3H), 6.89-6.84 (m, 2H), 5.79
(d, J = 11.2 Hz, 1H), 3.57 (dd, J = 3.2, 11.2 Hz, 1H), 2.50-2.41
(m, 1H), 2.36 (s, 3H), 2.07-2.04 (m, 1H), 1.88-1.49 (m, 4H),
1.42-1.25 (m, 2H), 0.96-0.84 (m, 2H), 0.74-0.64 (m, 1H);
13C{1H} NMR (100 MHz, CDCl3): δ 192.9, 145.1, 136.8, 133.0,
129.8 (2x), 129.4 (2x), 129.0, 128.7, 128.21 (4x), 128.20 (2x),
127.5 (2x), 126.7, 70.7, 51.3, 38.4, 32.3, 27.4, 26.7, 26.3, 26.2,
21.5.
3-Biphenyl-4-yl-3-cyclohexyl-1-phenyl-2-(toluene-4-
sulfonyl)propan-1-one (3e). 3e was synthesized according to
general synthetic procedure from 4n (438 mg, 1.0 mmol) and
cC6H11MgBr (2 mL, 1.0 M in THF, 2.0 mmol). Yield = 79%
9
o
(413 mg); Colorless solid; mp = 233-235 C (recrystallized
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11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
from hexanes and EtOAc); HRMS (ESI-TOF) m/z: [M + H]+
1
calcd for C34H35O3S 523.2307, found 523.2305; H NMR (400
MHz, CDCl3): δ 7.72 (d, J = 8.4 Hz, 2H), 7.59-7.57 (m, 3H),
7.46-7.22 (m, 11H), 6.95 (d, J = 8.0 Hz, 2H), 5.82 (d, J = 11.2
Hz, 1H), 3.63 (dd, J = 2.8, 11.2 Hz, 1H), 2.52-2.47 (m, 1H),
2.36 (s, 3H), 2.10-2.05 (m, 1H), 1.79-1.30 (m, 6H), 1.02-0.88
(m, 2H), 0.81-0.72 (m, 1H); 13C{1H} NMR (100 MHz, CDCl3):
δ 193.0, 145.2, 140.4, 139.4, 137.7, 135.9, 135.0, 133.1, 130.2
(2x), 129.8 (2x), 129.4 (2x), 128.6 (2x), 128.2 (4x), 127.1,
126.8 (2x), 126.2 (2x), 70.7, 51.0, 38.5, 32.3, 27.4, 26.7, 26.3,
16.2, 21.6.
3-Cyclohexyl-3-(4-methoxyphenyl)-1-phenyl-2-(toluene-4-
sulfonyl)propan-1-one (3b). 3b was synthesized according to
general synthetic procedure from 4d (392 mg, 1.0 mmol) and
cC6H11MgBr (2 mL, 1.0 M in THF, 2.0 mmol). Yield = 85%
o
(405 mg); Colorless solid; mp = 182-184 C (recrystallized
from hexanes and EtOAc); HRMS (ESI-TOF) m/z: [M + H]+
1
calcd for C29H33O4S 477.2100, found 477.2101; H NMR (400
MHz, CDCl3): δ 7.70 (d, J = 8.0 Hz, 2H), 7.56 (dd, J = 0.8, 8.0
Hz, 2H), 7.43-7.39 (m, 1H), 7.28-7.24 (m, 2H), 7.21 (d, J = 8.0
Hz, 2H), 6.80 (d, J = 8.4 Hz, 2H), 6.52 (d, J = 8.4 Hz, 2H),
5.74 (d, J = 11.6 Hz, 1H), 3.62 (s, 3H), 3.53 (dd, J = 3.2, 11.2
Hz, 1H), 2.45-2.37 (m, 1H), 2.34 (s, 3H), 2.04-2.01 (m, 1H),
1.75-1.49 (m, 4H), 1.42-1.25 (m, 2H), 0.99-0.84 (m, 2H), 0.74-
0.64 (m, 1H); 13C{1H} NMR (100 MHz, CDCl3): δ 192.9,
158.1, 145.1, 137.6, 135.1, 133.0, 130.7, 129.7 (2x), 129.4 (2x),
128.7 (2x), 128.2 (4x), 112.9 (2x), 70.8, 54.9, 50.4, 38.6, 32.2,
27.3, 26.6, 26.2 (2x), 21.5.
3-Cyclohexyl-3-naphthalen-2-yl-1-phenyl-2-(toluene-4-
sulfonyl)propan-1-one (3f). 3f was synthesized according to
general synthetic procedure from 4g (412 mg, 1.0 mmol) and
cC6H11MgBr (2 mL, 1.0 M in THF, 2.0 mmol). Yield = 78%
o
(387 mg); Colorless solid; mp = 213-214 C (recrystallized
from hexanes and EtOAc); HRMS (ESI-TOF) m/z: [M + H]+
1
calcd for C32H33O3S 497.2150, found 497.2150; H NMR (400
MHz, CDCl3): δ 8.20-8.18 (m, 2H), 7.81-7.80 (m, 1H), 7.73-
7.53 (m, 6H), 7.48-7.43 (m, 2H), 7.30 (br s, 1H), 7.22-7.18 (m,
1H), 7.13 (d, J = 8.4 Hz, 2H), 6.79 (d, J = 8.0 Hz, 1H), 5.90 (d,
J = 11.6 Hz, 1H), 3.77 (d, J = 11.2 Hz, 1H), 2.18 (s, 3H), 1.63-
1.29 (m, 6H), 1.20-1.08 (m, 1H), 0.98-0.82 (m, 1H), 0.78-0.61
(m, 2H), 0.55-0.45 (m, 1H); 13C{1H} NMR (100 MHz, CDCl3):
δ 193.4, 144.3, 138.2, 133.8, 133.0, 132.6, 132.5, 129.9, 129.0
(2x), 128.8 (4x), 128.7 (4x), 127.7, 127.4, 126.8, 125.7 (2x),
72.2, 51.6, 40.7, 32.0, 27.8, 26.2, 26.1, 25.7, 21.4.
3-Cyclohexyl-1-phenyl-2-(toluene-4-sulfonyl)-3-p-
tolylpropan-1-one (3c). 3c was synthesized according to gen-
eral synthetic procedure from 4o (376 mg, 1.0 mmol) and
cC6H11MgBr (2 mL, 1.0 M in THF, 2.0 mmol). Yield = 80%
o
(368 mg); Colorless solid; mp = 219-221 C (recrystallized
from hexanes and EtOAc); HRMS (ESI-TOF) m/z: [M + H]+
1
calcd for C29H33O3S 461.2150, found 461.2152; H NMR (400
MHz, CDCl3): δ 7.71 (d, J = 8.0 Hz, 2H), 7.58 (d, J = 8.4 Hz,
2H), 7.45-7.41 (m, 1H), 7.29-7.26 (m, 2H), 7.22 (d, J = 8.0 Hz,
2H), 6.80 (d, J = 8.4 Hz, 2H), 6.77 (d, J = 8.4 Hz, 2H), 5.78 (d,
J = 11.2 Hz, 1H), 3.55 (dd, J = 3.2, 11.2 Hz, 1H), 2.48-2.39 (m,
1H), 2.36 (s, 3H), 2.14 (s, 3H), 2.06-2.03 (m, 1H), 1.76-1.51
(m, 4H), 1.42-1.28 (m, 2H), 0.97-0.85 (m, 2H), 0.75-0.65 (m,
1H); 13C{1H} NMR (100 MHz, CDCl3): δ 192.9, 145.1, 137.7,
136.2, 135.1, 133.7, 132.9, 129.8 (2x), 129.6 (2x), 129.4 (2x),
128.3 (2x), 128.24 (2x), 128.16 (2x), 70.7, 50.8, 38.5, 32.2,
27.4, 26.7, 26.3, 26.2, 21.5, 20.8.
3-Cyclohexyl-3-(3,4-dimethoxyphenyl)-1-phenyl-2-(toluene-
4-sulfonyl)propan-1-one (3g). 3g was synthesized according to
general synthetic procedure from 4a (422 mg, 1.0 mmol) and
cC6H11MgBr (2 mL, 1.0 M in THF, 2.0 mmol). Yield = 80%
(405 mg); Colorless liquid; HRMS (ESI-TOF) m/z: [M + H]+
1
calcd for C30H35O5S 507.2205, found 507.2203; H NMR (400
MHz, CDCl3): δ 7.71 (d, J = 8.0 Hz, 2H), 7.60-7.58 (m, 2H),
7.45-7.38 (m, 1H), 7.29 (d, J = 8.0 Hz, 2H), 7.23 (d, J = 8.0 Hz,
2H), 6.50 (d, J = 8.0 Hz, 1H), 6.42 (dd, J = 2.0, 8.4 Hz, 1H),
6.31 (d, J = 1.6 Hz, 1H), 5.74 (d, J = 11.6 Hz, 1H), 3.71 (s, 3H),
3.50-3.47 (m, 1H), 3.50 (s, 3H), 2.45-2.37 (m, 1H), 2.36 (s,
3H), 2.04-2.00 (m, 1H), 1.76-1.20 (m, 6H), 0.99-0.85 (m, 2H),
0.79-0.69 (m, 1H); 13C{1H} NMR (100 MHz, CDCl3): δ 192.8,
147.7, 147.6, 145.1, 137.8, 135.0, 133.0, 129.8 (2x), 129.4 (2x),
129.2, 128.3 (2x), 128.2 (2x), 122.3, 113.0, 110.2, 70.7, 55.6,
55.4, 50.9, 38.5, 32.3, 27.4, 26.7, 26.3, 26.2, 21.6.
3-Cyclohexyl-3-(4-fluorophenyl)-1-phenyl-2-(toluene-4-
sulfonyl)propan-1-one (3d). 3d was synthesized according to
general synthetic procedure from 4j (380 mg, 1.0 mmol) and
cC6H11MgBr (2 mL, 1.0 M in THF, 2.0 mmol). Yield = 83%
o
(385 mg); Colorless solid; mp = 195-197 C (recrystallized
from hexanes and EtOAc); HRMS (ESI-TOF) m/z: [M + H]+
calcd for C28H30FO3S 465.1900, found 465.1903; 1H NMR
(400 MHz, CDCl3): δ 7.69 (d, J = 8.4 Hz, 2H), 7.57-7.55 (m,
2H), 7.46-7.42 (m, 1H), 7.29 (d, J = 8.0 Hz, 2H), 7.22 (d, J =
8.4 Hz, 2H), 6.87-6.83 (m, 2H), 6.71-6.66 (m, 2H), 5.72 (d, J =
11.2 Hz, 1H), 3.57 (dd, J = 3.6, 11.2 Hz, 1H), 2.48-2.40 (m,
1H), 2.35 (s, 3H), 2.04-2.01 (m, 1H), 1.76-1.50 (m, 4H), 1.42-
1.24 (m, 2H), 0.95-0.82 (m, 2H), 0.70-0.60 (m, 1H); 13C{1H}
NMR (100 MHz, CDCl3): δ 192.8, 161.5 (d, J = 244.1 Hz),
3-Benzo[1,3]dioxol-5-yl-3-cyclohexyl-1-phenyl-2-(toluene-
4-sulfonyl)propan-1-one (3h). 3h was synthesized according to
general synthetic procedure from 4b (406 mg, 1.0 mmol) and
cC6H11MgBr (2 mL, 1.0 M in THF, 2.0 mmol). Yield = 82%
o
(402 mg); Colorless solid; mp = 115-117 C (recrystallized
from hexanes and EtOAc); HRMS (ESI-TOF) m/z: [M + H]+
1
calcd for C29H31O5S 491.1892, found 491.1895; H NMR (400
MHz, CDCl3): δ 7.68 (d, J = 8.4 Hz, 2H), 7.69-7.57 (m, 2H),
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The Journal of Organic Chemistry
7.45-7.41 (m, 1H), 7.29 (d, J = 7.6 Hz, 2H), 7.20 (d, J = 8.0 Hz,
3-(3,4-Dimethoxyphenyl)-3-(4-methoxyphenyl)-1-phenyl-2-
2
3
4
5
6
7
8
9
2H), 6.43 (d, J = 8.0 Hz, 1H), 6.39 (d, J = 1.2 Hz, 1H), 6.33
(dd, J = 1.2, 8.0 Hz, 1H), 5.79 (d, J = 1.2 Hz, 1H), 5.75 (d, J =
0.8 Hz, 1H), 5.69 (d, J = 11.2 Hz, 1H), 3.50 (dd, J = 3.2, 11.2
Hz, 1H), 2.49-2.36 (m, 1H), 2.34 (s, 3H), 2.04-2.00 (m, 1H),
1.76-1.20 (m, 6H), 0.99-0.85 (m, 2H), 0.79-0.69 (m, 1H);
13C{1H} NMR (100 MHz, CDCl3): δ 192.7, 146.9, 146.2, 145.1,
137.6, 135.0, 133.0, 130.5, 129.8 (2x), 129.4 (2x), 128.24 (2x),
128.20 (2x), 122.8, 110.3, 107.3, 100.7, 70.7, 50.9, 38.5, 32.3,
27.4, 26.6, 26.2 (2x), 21.5.
(toluene-4-sulfonyl)propan-1-one (3l). 3l was synthesized ac-
cording to general synthetic procedure from 4a (422 mg, 1.0
mmol) and 4-MeOC6H4MgBr (2 mL, 1.0 M in THF, 2.0 mmol).
o
Yield = 70% (371 mg); Colorless solid; mp = 204-206 C (re-
crystallized from hexanes and EtOAc); HRMS (ESI-TOF) m/z:
[M + H]+ calcd for C31H31O6S 531.1841, found 531.1842; H
1
NMR (400 MHz, CDCl3): δ 7.84 (d, J = 7.2 Hz, 2H), 7.53-7.50
(m, 1H), 7.41-7.37 (m, 4H), 7.21 (d, J = 8.8 Hz, 2H), 7.12 (d, J
= 8.0 Hz, 2H), 6.71 (d, J = 7.6 Hz, 2H), 6.64 (dd, J = 2.0, 8.4
Hz, 1H), 6.56 (d, J = 2.0 Hz, 1H), 6.50 (d, J = 8.4 Hz, 1H),
6.05 (d, J = 11.6 Hz, 1H), 4.76 (d, J = 12.0 Hz, 1H), 3.75 (s,
3H), 3.65 (s, 3H), 3.56 (s, 3H), 2.37 (s, 3H); 13C{1H} NMR
(100 MHz, CDCl3): δ 192.3, 158.6, 148.6, 147.6, 144.6, 137.9,
135.8, 133.5, 133.3, 131.5, 129.4 (2x), 129.2 (2x), 129.1 (2x),
128.5 (2x), 128.4 (2x), 119.6, 113.8 (2x), 111.2, 111.0, 73.2,
55.6, 55.5, 55.1, 50.7, 21.5.
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15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
3-Cyclohexyl-1-phenyl-2-(toluene-4-sulfonyl)-3-(3,4,5-
trimethoxyphenyl)propan-1-one (3i). 3i was synthesized ac-
cording to general synthetic procedure from 4e (452 mg, 1.0
mmol) and cC6H11MgBr (2 mL, 1.0 M in THF, 2.0 mmol).
o
Yield = 78% (418 mg); Colorless solid; mp = 180-181 C (re-
crystallized from hexanes and EtOAc); HRMS (ESI-TOF) m/z:
[M + H]+ calcd for C31H37O6S 537.2311, found 537.2312; H
1
NMR (400 MHz, CDCl3): δ 7.72 (d, J = 8.0 Hz, 2H), 7.59-7.57
(m, 2H), 7.45-7.41 (m, 1H), 7.29 (d, J = 8.0 Hz, 2H), 7.26-7.23
(m, 2H), 5.99 (s, 2H), 5.72 (d, J = 11.2 Hz, 1H), 3.67 (s, 3H),
3.47-3.44 (m, 6H), 2.45-2.38 (m, 1H), 2.36 (s, 3H), 2.03-1.97
(m, 1H), 1.76-1.50 (m, 5H), 1.42-1.23 (m, 2H), 0.99-0.75 (m,
3H); 13C{1H} NMR (100 MHz, CDCl3): δ 192.8, 152.1, 145.2
(2x), 138.1, 136.7, 135.1, 133.0 (2x), 132.2, 129.8 (2x), 129.5
(2x), 128.3 (2x), 128.1 (2x), 107.3, 70.7, 60.7, 55.7 (2x), 51.7,
38.4, 32.4, 27.4, 26.7, 26.3, 26.2, 21.6.
3-(3,4-Dimethoxyphenyl)-1-phenyl-2-(toluene-4-sulfonyl)-3-
p-tolylpropan-1-one (3m). 3m was synthesized according to
general synthetic procedure from 4a (422 mg, 1.0 mmol) and
4-MeC6H4MgBr (2 mL, 1.0 M in THF, 2.0 mmol). Yield =
o
74% (380 mg); Colorless solid; mp = 188-190 C (recrystal-
lized from hexanes and EtOAc); HRMS (ESI-TOF) m/z: [M +
1
H]+ calcd for C31H31O5S 515.1892, found 515.1893; H NMR
(400 MHz, CDCl3): δ 7.84 (d, J = 8.4 Hz, 2H), 7.55-7.51 (m,
1H), 7.43-7.39 (m, 2H), 7.36 (d, J = 8.4 Hz, 2H), 7.12 (d, J =
8.0 Hz, 2H), 6.99 (d, J = 8.0 Hz, 2H), 6.88 (dd, J = 2.0, 8.0 Hz,
1H), 6.82 (d, J = 8.0 Hz, 2H), 6.66 (d, J = 8.4 Hz, 1H), 6.64 (d,
J = 2.0 Hz, 1H), 6.03 (d, J = 11.6 Hz, 1H), 4.77 (d, J = 12.0 Hz,
1H), 3.82 (s, 3H), 3.77 (s, 3H), 2.38 (s, 3H), 2.10 (s, 3H);
13C{1H} NMR (100 MHz, CDCl3): δ 192.3, 148.6, 148.1, 144.5,
137.7, 136.5, 133.3, 131.8, 129.3 (2x), 129.14 (2x), 129.06 (2x),
128.52 (2x), 128.46 (2x), 124.4, 128.2, 127.4 (2x), 120.7, 111.8,
111.0, 73.4, 55.8, 55.7, 51.2, 21.5, 20.8.
3-(3,4-Dimethoxyphenyl)-1,3-diphenyl-2-(toluene-4-
sulfonyl)propan-1-one (3j). 3j was synthesized according to
general synthetic procedure from 4a (422 mg, 1.0 mmol) and
PhMgBr (2 mL, 1.0 M in THF, 2.0 mmol). Yield = 73% (365
o
mg); Colorless solid; mp = 203-205 C (recrystallized from
hexanes and EtOAc); HRMS (ESI-TOF) m/z: [M + H]+ calcd
1
for C30H29O5S 501.1736, found 501.1735; H NMR (400 MHz,
CDCl3): δ 7.84 (d, J = 8.4 Hz, 2H), 7.55-7.51 (m, 1H), 7.43-
7.29 (m, 6H), 7.22-7.17 (m, 3H), 7.12 (d, J = 8.0 Hz, 2H), 6.66
(dd, J = 2.0, 8.4 Hz, 1H), 6.57 (d, J = 2.4 Hz, 1H), 6.50 (d, J =
8.4 Hz, 1H), 6.08 (d, J = 11.6 Hz, 1H), 4.79 (d, J = 12.0 Hz,
1H), 3.66 (s, 3H), 3.57 (s, 3H), 2.38 (s, 3H); 13C{1H} NMR
(100 MHz, CDCl3): δ 192.3, 148.7, 147.7, 144.7, 139.5, 138.0,
135.7, 133.4, 133.2, 129.3 (2x), 129.2 (2x), 128.6 (2x), 128.5
(2x), 128.43 (2x), 128.40 (2x), 127.1, 119.9, 111.2, 111.1, 75.4,
55.7, 55.6, 51.5, 21.6.
3-(3,4-Dimethoxyphenyl)-1-phenyl-2-(toluene-4-sulfonyl)-3-
o-tolyl-propan-1-one (3n). 3n was synthesized according to
general synthetic procedure from 4a (422 mg, 1.0 mmol) and
2-MeC6H4MgBr (2 mL, 1.0 M in THF, 2.0 mmol). Yield =
o
67% (345 mg); Colorless solid; mp = 153-155 C (recrystal-
lized from hexanes and EtOAc); HRMS (ESI-TOF) m/z: [M +
1
H]+ calcd for C31H31O5S 515.1892, found 515.1896; H NMR
(400 MHz, CDCl3): δ 7.84-7.82 (m, 2H), 7.54-7.49 (m, 1H),
7.42-7.37 (m, 4H), 7.12-7.08 (m, 3H), 6.97-6.79 (m, 4H), 6.72
(d, J = 2.0 Hz, 1H), 6.64 (d, J = 4.0 Hz, 1H), 6.07 (d, J = 10.8
Hz, 1H), 5.22 (d, J = 12.0 Hz, 1H), 3.81 (s, 3H), 3.75 (s, 3H),
2.40 (s, 3H), 2.35 (s, 3H); 13C{1H} NMR (100 MHz, CDCl3): δ
192.0, 148.6, 148.2, 144.4, 139.1, 137.7, 136.6, 135.9, 133.2,
131.0, 130.8, 129.1 (2x), 128.8 (2x), 128.5 (2x), 128.3 (2x),
126.7, 125.9, 125.6, 121.6, 112.3, 110.9, 74.0, 55.8, 55.7, 45.9,
21.5, 20.0.
3-(3,4-Dimethoxyphenyl)-3-(4-fluorophenyl)-1-phenyl-2-
(toluene-4-sulfonyl)propan-1-one (3k). 3k was synthesized
according to general synthetic procedure from 4a (422 mg, 1.0
mmol) and 4-FC6H4MgBr (2 mL, 1.0 M in THF, 2.0 mmol).
o
Yield = 72% (373 mg); Colorless solid; mp = 199-201 C (re-
crystallized from hexanes and EtOAc); HRMS (ESI-TOF) m/z:
1
[M + H]+ calcd for C30H28FO5S 519.1642, found 519.1643; H
NMR (400 MHz, CDCl3): δ 7.83-7.81 (m, 2H), 7.55-7.51 (m,
1H), 7.42-7.38 (m, 4H), 7.30-7.26 (m, 2H), 7.15 (d, J = 8.4 Hz,
2H), 6.91-6.86 (m, 2H), 6.64 (dd, J = 2.0, 8.4 Hz, 1H), 6.55 (d,
J = 2.0 Hz, 1H), 6.51 (d, J = 8.4 Hz, 1H), 6.03 (d, J = 12.0 Hz,
1H), 4.81 (d, J = 12.0 Hz, 1H), 3.67 (s, 3H), 3.57 (s, 3H), 2.38
(s, 3H); 13C{1H} NMR (100 MHz, CDCl3): δ 192.1, 161.9 (d, J
= 244.8 Hz), 148.7, 147.8, 144.9, 137.8, 135.7, 135.4 (d, J =
3.0 Hz), 133.5, 132.9, 130.0, 129.9, 129.3 (2x), 129.2 (2x),
128.6 (2x), 128.4 (2x), 119.7, 115.3 (d, J = 21.2 Hz, 2x), 111.1
(d, J = 21.2 Hz, 2x), 73.2, 55.7, 55.6, 50.6, 21.6.
3-(3,4-Dimethoxyphenyl)-1-phenyl-2-(toluene-4-
sulfonyl)butan-1-one (3o). 3o was synthesized according to
general synthetic procedure from 4a (422 mg, 1.0 mmol) and
MeMgBr (2 mL, 1.0 M in THF, 2.0 mmol). Yield = 63% (276
mg); Colorless liquid; HRMS (ESI-TOF) m/z: [M + H]+ calcd
1
for C25H27O5S 439.1579, found 439.1580; H NMR (400 MHz,
CDCl3): δ 7.86-7.83 (m, 2H), 7.59-7.54 (m, 1H), 7.45-7.42 (m,
4H), 7.12 (d, J = 8.0 Hz, 2H), 6.70-6.65 (m, 2H), 6.52 (d, J =
1.6 Hz, 1H), 5.32 (d, J = 8.8 Hz, 1H), 3.89-3.75 (m, 1H), 3.83
(s, 3H), 3.71 (s, 3H), 2.35 (s, 3H), 1.20 (d, J = 7.2 Hz, 3H);
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13C{1H} NMR (100 MHz, CDCl3): δ 193.0, 148.7, 148.1, 144.5,
137.7, 136.2, 134.0, 133.7, 129.2 (2x), 128.9 (2x), 128.7 (2x),
128.6 (2x), 120.0, 111.01, 110.98, 75.4, 55.8, 55.6, 40.0, 21.5,
20.3.
NMR (400 MHz, CDCl3): δ 7.69 (d, J = 8.0 Hz, 2H), 7.50 (d, J
= 8.4 Hz, 2H), 7.21 (d, J = 7.6 Hz, 2H), 7.06 (d, J = 7.6 Hz,
2H), 6.49 (d, J = 8.0 Hz, 1H), 6.42 (d, J = 8.4 Hz, 1H), 6.32 (s,
1H), 5.71 (d, J = 11.2 Hz, 1H), 3.70 (s, 3H), 3.50 (s, 3H), 3.49-
3.46 (m, 1H), 2.43-2.36 (m, 1H), 2.34 (s, 3H), 2.31 (s, 3H),
2.03-2.01 (m, 1H), 1.74-1.20 (m, 6H), 0.99-0.85 (m, 2H), 0.78-
0.68 (m, 1H); 13C{1H} NMR (100 MHz, CDCl3): δ 192.2,
147.6, 147.5, 145.0, 144.0, 135.3, 135.1, 129.7 (2x), 129.32
(2x), 129.25, 128.9 (2x), 128.4 (2x), 122.2, 112.9, 110.1, 70.5,
55.5, 55.4, 50.8, 38.5, 32.3, 27.4, 26.6, 26.23, 26.21, 21.50,
21.48.
3-(3,4-Dimethoxyphenyl)-4-methyl-1-phenyl-2-(toluene-4-
sulfonyl)pentan-1-one (3p). 3p was synthesized according to
general synthetic procedure from 4a (422 mg, 1.0 mmol) and i-
PrMgBr (2 mL, 1.0 M in THF, 2.0 mmol). Yield = 80% (373
mg); Colorless liquid; HRMS (ESI-TOF) m/z: [M + H]+ calcd
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
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for C27H31O5S 467.1892, found 467.1893; H NMR (400 MHz,
CDCl3): δ 7.69 (d, J = 8.0 Hz, 2H), 7.59-7.57 (m, 2H), 7.44-
7.40 (m, 1H), 7.29-7.25 (m, 2H), 7.21 (d, J = 8.0 Hz, 2H), 6.51
(d, J = 8.4 Hz, 1H), 6.44 (dd, J = 2.0, 8.4 Hz, 1H), 6.33 (d, J =
1.6 Hz, 1H), 5.66 (d, J = 11.2 Hz, 1H), 3.70 (s, 3H), 3.52-3.49
(m, 1H), 3.49 (s, 3H), 2.88-2.82 (m, 1H), 2.34 (s, 3H), 0.99 (d,
J = 6.8 Hz, 3H), 0.78 (d, J = 6.8 Hz, 3H); 13C{1H} NMR (100
MHz, CDCl3): δ 192.8, 147.71, 177.67, 145.1 (2x), 137.7,
134.8, 133.0, 129.9 (2x), 129.4 (2x), 128.3 (2x), 128.2 (2x),
122.5, 113.2, 110.2, 71.6, 55.5, 55.4, 50.7, 28.1, 21.6, 21.5,
16.5.
3-Cyclohexyl-3-(3,4-dimethoxyphenyl)-1-(4-methoxyphenyl)-
2-(toluene-4-sulfonyl)propan-1-one (3t). 3t was synthesized
according to general synthetic procedure from 4u (452 mg, 1.0
mmol) and cC6H11MgBr (2 mL, 1.0 M in THF, 2.0 mmol).
Yield = 80% (429 mg); Colorless solid; mp = 96-98 oC (recrys-
tallized from hexanes and EtOAc); HRMS (ESI-TOF) m/z: [M
+ H]+ calcd for C31H37O6S 537.2311, found 537.2310; 1H NMR
(400 MHz, CDCl3): δ 7.69 (d, J = 8.4 Hz, 2H), 7.61 (d, J = 9.2
Hz, 2H), 7.22 (d, J = 8.0 Hz, 2H), 7.76 (d, J = 8.8 Hz, 2H),
6.50 (d, J = 8.1 Hz, 1H), 6.43 (dd, J = 2.0, 8.4 Hz, 1H), 6.35 (d,
J = 1.6 Hz, 1H), 5.68 (d, J = 11.2 Hz, 1H), 3.80 (s, 3H), 3.71 (s,
3H), 3.55 (s, 3H), 3.48 (dd, J = 3.2, 11.2 Hz, 1H), 2.43-2.36 (m,
1H), 2.36 (s, 3H), 2.04-2.00 (m, 1H), 1.82-1.30 (m, 6H), 1.04-
0.85 (m, 2H), 0.79-0.69 (m, 1H); 13C{1H} NMR (100 MHz,
CDCl3): δ 190.9, 163.5, 147.6, 147.5, 145.0, 135.1, 130.9,
130.7 (2x), 129.8 (2x), 129.4, 129.3 (2x), 122.2, 113.5 (2x),
113.1, 110.1, 70.4, 55.55, 55.48, 55.46, 50.7, 38.6, 32.4, 27.5,
26.7, 26.29, 26.26, 21.6.
3-Cyclopentyl-3-(3,4-dimethoxyphenyl)-1-phenyl-2-(toluene-
4-sulfonyl)propan-1-one (3q). 3q was synthesized according to
general synthetic procedure from 4a (422 mg, 1.0 mmol) and
cC5H9MgBr (2 mL, 1.0 M in THF, 2.0 mmol). Yield = 83%
(409 mg); Colorless liquid; HRMS (ESI-TOF) m/z: [M + H]+
1
calcd for C29H33O5S 493.2049, found 493.2048; H NMR (400
MHz, CDCl3): δ 7.66-7.61 (m, 4H), 7.47-7.43 (m, 1H), 7.33-
7.27 (m, 2H), 7.18 (d, J = 8.0 Hz, 2H), 6.53 (d, J = 8.4 Hz, 1H),
6.49 (dd, J = 1.2, 8.4 Hz, 1H), 6.41 (br s, 1H), 5.60 (d, J = 9.6
Hz, 1H), 3.72 (s, 3H), 3.69 (dd, J = 5.6, 9.6 Hz, 1H), 3.52 (s,
3H), 2.78-2.71 (m, 1H), 2.34 (s, 3H), 1.82-1.63 (m, 2H), 1.50-
1.05 (m, 6H); 13C{1H} NMR (100 MHz, CDCl3): δ 192.8,
147.8, 147.7, 145.0, 137.8, 135.0, 133.1, 129.8 (2x), 129.6,
129.3 (2x), 128.4 (2x), 125.3 (2x), 122.5, 113.2, 110.2, 73.2,
55.6, 55.4, 48.2, 41.8, 30.5, 27.5, 24.6, 24.3, 21.5.
3-Cyclohexyl-3-(3,4-dimethoxyphenyl)-2-(toluene-4-
sulfonyl)-1-(4-trifluoromethylphenyl)propan-1-one (3u). 3u
was synthesized according to general synthetic procedure from
4w (490 mg, 1.0 mmol) and cC6H11MgBr (2 mL, 1.0 M in THF,
2.0 mmol). Yield = 86% (494 mg); Colorless solid; mp = 149-
151 oC (recrystallized from hexanes and EtOAc); HRMS (ESI-
TOF) m/z: [M + H]+ calcd for C31H34F3O5S 575.2079, found
3-Cyclohexyl-3-(3,4-dimethoxyphenyl)-1-(4-fluorophenyl)-2-
(toluene-4-sulfonyl)propan-1-one (3r). 3r was synthesized
according to general synthetic procedure from 4t (440 mg, 1.0
mmol) and cC6H11MgBr (2 mL, 1.0 M in THF, 2.0 mmol).
1
575.2080; H NMR (400 MHz, CDCl3): δ 7.70 (d, J = 8.4 Hz,
2H), 7.69 (d, J = 8.0 Hz, 2H), 7.55 (d, J = 8.4 Hz, 2H), 7.25 (d,
J = 8.0 Hz, 2H), 6.48 (d, J = 8.0 Hz, 1H), 6.38 (dd, J = 2.0, 8.4
Hz, 1H), 6.29 (d, J = 1.6 Hz, 1H), 5.68 (d, J = 11.2 Hz, 1H),
3.71 (s, 3H), 3.53 (s, 3H), 3.47 (d, J = 3.2, 11.2 Hz, 1H), 2.44-
2.36 (m, 1H), 2.37 (s, 3H), 2.03-2.01 (m, 1H), 1.74-1.20 (m,
6H), 0.98-0.85 (m, 2H), 0.78-0.67 (m, 1H); 13C{1H} NMR (100
MHz, CDCl3): δ 192.2, 147.9, 147.8, 145.5, 140.4, 134.9,
134.6 (q, J = 32.6 Hz), 129.7 (2x), 129.6 (2x), 128.9, 128.5
(2x), 125.8 (q, J = 224.4 Hz), 125.3 (q, J = 3.8 Hz, 2x), 122.0,
113.2, 110.2, 71.6, 55.6, 55.5, 50.9, 38.5, 32.3, 27.3, 26.6,
26.21, 26.19, 21.5.
o
Yield = 82% (430 mg); Colorless solid; mp = 166-168 C (re-
crystallized from hexanes and EtOAc); HRMS (ESI-TOF) m/z:
1
[M + H]+ calcd for C30H34FO5S 525.2111, found 525.2112; H
NMR (400 MHz, CDCl3): δ 7.70 (d, J = 8.4 Hz, 2H), 7.67-7.63
(m, 2H), 7.25 (d, J = 8.4 Hz, 2H), 6.99-6.95 (m, 2H), 6.50 (d, J
= 8.0 Hz, 1H), 6.39 (dd, J = 2.0, 8.4 Hz, 1H), 6.32 (d, J = 1.6
Hz, 1H), 5.67 (d, J = 11.6 Hz, 1H), 3.72 (s, 3H), 3.56 (s, 3H),
3.46 (dd, J = 3.2, 11.2 Hz, 1H), 2.38 (s, 3H), 2.45-2.37 (m, 1H),
2.04-2.00 (m, 1H), 1.76-1.20 (m, 6H), 1.06-0.85 (m, 2H), 0.78-
0.68 (m, 1H); 13C{1H} NMR (100 MHz, CDCl3): δ 191.3,
165.6 (d, J = 254.7 Hz), 147.8, 147.7, 145.3, 134.9, 134.2,
131.0 (d, J = 9.1 Hz, 2x), 129.8 (2x), 120.5 (2x), 129.2, 122.0,
115.5 (d, J = 22.0 Hz, 2x), 113.1, 110.1, 71.0, 55.6, 55.5, 50.9,
38.5, 32.3, 27.4, 26.7, 26.3, 26.2, 21.6.
1-Biphenyl-4-yl-3-cyclohexyl-3-(3,4-dimethoxyphenyl)-2-
(toluene-4-sulfonyl)propan-1-one (3v). 3v was synthesized
according to general synthetic procedure from 4y (498 mg, 1.0
mmol) and cC6H11MgBr (2 mL, 1.0 M in THF, 2.0 mmol).
o
Yield = 85% (495 mg); Colorless solid; mp = 134-136 C (re-
crystallized from hexanes and EtOAc); HRMS (ESI-TOF) m/z:
3-Cyclohexyl-3-(3,4-dimethoxyphenyl)-2-(toluene-4-
1
[M + H]+ calcd for C36H39O5S 583.2518, found 583.2517; H
sulfonyl)-1-p-tolylpropan-1-one (3s). 3s was synthesized ac-
cording to general synthetic procedure from 4v (436 mg, 1.0
mmol) and cC6H11MgBr (2 mL, 1.0 M in THF, 2.0 mmol).
NMR (400 MHz, CDCl3): δ 7.74 (d, J = 8.4 Hz, 2H), 7.69 (d, J
= 8.4 Hz, 2H), 7.56-7.37 (m, 7H), 7.24 (d, J = 8.0 Hz, 2H),
6.52 (d, J = 8.4 Hz, 1H), 6.46 (dd, J = 1.6, 8.0 Hz, 1H), 6.36 (s,
1H), 5.78 (d, J = 11.2 Hz, 1H), 3.71 (s, 3H), 3.54-3.47 (m, 1H),
3.52 (s, 3H), 2.47-2.40 (m, 1H), 2.35 (s, 3H), 2.07-2.02 (m,
o
Yield = 84% (437 mg); Colorless solid; mp = 118-121 C (re-
crystallized from hexanes and EtOAc); HRMS (ESI-TOF) m/z:
1
[M + H]+ calcd for C31H37O5S 521.2362, found 521.2361; H
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The Journal of Organic Chemistry
1H), 1.90-1.57 (m, 4H), 1.39-1.17 (m, 2H), 1.06-0.85 (m, 2H),
(ESI-TOF) m/z: [M + H]+ calcd for C30H35O6S 523.2154, found
523.2154; H NMR (400 MHz, CDCl3): δ 7.73 (d, J = 8.8 Hz,
2
3
4
5
6
7
0.81-0.71 (m, 1H); 13C{1H} NMR (100 MHz, CDCl3): δ 192.3,
147.7, 147.6, 145.7, 145.1, 139.4, 136.5, 135.0, 129.8 (2x),
129.4 (2x), 129.3, 128.93 (2x), 128.85 (2x), 128.4, 127.1 (2x),
126.8 (2x), 122.2, 113.1, 110.2, 70.8, 55.5, 55.4, 50.8, 38.5,
32.3, 27.4, 26.7, 26.3, 26.2, 21.6.
1
2H), 7.59-7.57 (m, 2H), 7.43-7.39 (m, 1H), 7.29-7.25 (m, 2H),
6.87 (d, J = 8.8 Hz, 2H), 6.49 (d, J = 8.4 Hz, 1H), 6.41 (dd, J =
2.0, 8.4 Hz, 1H), 6.31 (s, 1H), 5.73 (d, J = 11.6 Hz, 1H), 3.79
(s, 3H), 3.69 (s, 3H), 3.48 (br s, 3H), 3.47 (dd, J = 4.8, 11.6 Hz,
1H), 2.44-2.37 (m, 1H), 2.08-2.01 (m, 1H), 1.79-1.49 (m, 5H),
1.41-1.32 (m, 2H), 1.09-0.83 (m, 1H), 0.79-0.68 (m, 1H);
13C{1H} NMR (100 MHz, CDCl3): δ 192.9, 163.9, 147.64,
147.55, 137.8, 133.0, 132.0 (2x), 129.4, 129.2, 128.3 (2x),
128.1 (2x), 122.2, 113.9 (2x), 113.0, 110.1, 70.7, 55.6, 55.5,
55.4, 50.9, 38.5, 32.3, 27.3, 26.6, 26.3, 26.2.
3-Cyclohexyl-3-(3,4-dimethoxyphenyl)-1-naphthalen-2-yl-2-
(toluene-4-sulfonyl)propan-1-one (3w). 3w was synthesized
according to general synthetic procedure from 4z (472 mg, 1.0
mmol) and cC6H11MgBr (2 mL, 1.0 M in THF, 2.0 mmol).
Yield = 82% (456 mg); Colorless solid; mp = 92-94 oC (recrys-
tallized from hexanes and EtOAc); HRMS (ESI-TOF) m/z: [M
+ H]+ calcd for C34H37O5S 557.2362, found 557.2361; 1H NMR
(400 MHz, CDCl3): δ 8.17 (s, 1H), 7.89 (d, J = 8.0 Hz, 1H),
7.78 (d, J = 7.6 Hz, 1H), 7.73 (d, J = 8.4 Hz, 2H), 7.69 (d, J =
8.8 Hz, 1H), 7.59-7.51 (m, 3H), 7.18 (d, J = 8.0 Hz, 2H), 6.45
(s, 2H), 6.38 (s, 1H), 5.89 (d, J = 11.6 Hz, 1H), 3.65 (s, 3H),
3.56 (d, J = 3.6, 11.2 Hz, 1H), 3.44 (s, 3H), 2.51-2.42 (m, 1H),
2.26 (s, 3H), 2.26-2.10 (m, 1H), 1.79-1.30 (m, 6H), 1.00-0.85
(m, 2H), 0.82-0.72 (m, 1H); 13C{1H} NMR (100 MHz, CDCl3):
δ 192.7, 147.7, 147.6, 145.2, 135.3, 135.2, 135.0, 132.0, 130.1,
129.8 (2x), 129.6, 129.4 (2x), 129.3, 128.8, 128.2, 127.6, 126.9,
123.7, 122.1, 113.2, 110.1, 71.0, 55.5, 55.4, 51.0, 38.6, 32.4,
27.5, 26.7, 26.30, 26.27, 21.5.
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53
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59
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3-Cyclohexyl-3-(3,4-dimethoxyphenyl)-2-(4-
fluorobenzenesulfonyl)-1-phenylpropan-1-one (3aa). 3aa was
synthesized according to general synthetic procedure from 4ab
(426 mg, 1.0 mmol) and cC6H11MgBr (2 mL, 1.0 M in THF,
2.0 mmol). Yield = 82% (418 mg); Colorless solid; mp = 145-
147 oC (recrystallized from hexanes and EtOAc); HRMS (ESI-
TOF) m/z: [M + H]+ calcd for C29H32FO5S 511.1955, found
1
511.1956; H NMR (400 MHz, CDCl3): δ 7.85-7.82 (m, 2H),
7.59-7.57 (m, 2H), 7.45-7.42 (m, 1H), 7.30-7.26 (m, 2H), 7.11-
7.07 (m, 2H), 6.49 (d, J = 8.4 Hz, 1H), 6.42 (dd, J = 2.0, 8.4 Hz,
1H), 6.32 (s, 1H), 5.76 (d, J = 11.2 Hz, 1H), 3.69 (s, 3H), 3.49
(br s, 3H), 3.48 (dd, J = 4.8, 11.6 Hz, 1H), 2.41-2.34 (m, 1H),
2.08-2.02 (m, 1H), 1.77-1.49 (m, 5H), 1.40-1.22 (m, 1H), 1.01-
0.86 (m, 2H), 0.80-0.70 (m, 1H); 13C{1H} NMR (100 MHz,
CDCl3): δ 192.7, 165.9 (d, J = 256.2 Hz), 147.72, 147.68,
137.5, 133.89 (d, J = 3.0 Hz), 133.0, 132.7 (d, J = 9.8 Hz, 2x),
128.9, 128.4 (2x), 128.1 (2x), 122.2, 116.04 (d, J = 22.7 Hz,
2x), 113.0, 110.2, 70.7, 55.5, 55.4, 51.0, 38.7, 32.3, 27.4, 26.6,
26.23, 26.16.
2-Benzenesulfonyl-3-cyclohexyl-3-(3,4-dimethoxyphenyl)-1-
phenylpropan-1-one (3x). 3x was synthesized according to
general synthetic procedure from 4aa (408 mg, 1.0 mmol) and
cC6H11MgBr (2 mL, 1.0 M in THF, 2.0 mmol). Yield = 80%
o
(394 mg); Colorless solid; mp = 75-77 C (recrystallized from
hexanes and EtOAc); HRMS (ESI-TOF) m/z: [M + H]+ calcd
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for C29H33O5S 493.2049, found 493.2047; H NMR (400 MHz,
CDCl3): δ 7.85-7.82 (m, 2H), 7.58-7.56 (m, 2H), 7.53-7.49 (m,
1H), 7.44-7.38 (m, 3H), 7.28-7.24 (m, 2H), 6.49 (d, J = 8.4 Hz,
1H), 6.42 (dd, J = 2.0, 8.4 Hz, 1H), 6.31 (d, J = 1.6 Hz, 1H),
5.76 (d, J = 11.6 Hz, 1H), 3.69 (s, 3H), 3.54 (dd, J = 3.6, 11.6
Hz, 1H), 3.48 (s, 3H), 2.44-2.36 (m, 1H), 2.02-1.98 (m, 1H),
1.71-1.30 (m, 6H), 1.04-0.83 (m, 2H), 0.78-0.68 (m, 1H);
13C{1H} NMR (100 MHz, CDCl3): δ 192.6, 147.7, 147.6, 138.1,
137.6, 134.0, 133.1, 129.7 (2x), 129.0, 128.8 (2x), 128.3 (2x),
128.1 (2x), 122.2, 112.9, 110.1, 70.6, 55.5, 55.4, 50.9, 38.6,
32.2, 27.4, 26.6, 26.21, 26.17.
3-Cyclohexyl-3-(3,4-dimethoxyphenyl)-2-(4-
isopropylbenzenesulfonyl)-1-phenylpropan-1-one (3ab). 3ab
was synthesized according to general synthetic procedure from
4ap (450 mg, 1.0 mmol) and cC6H11MgBr (2 mL, 1.0 M in
THF, 2.0 mmol). Yield = 85% (454 mg); Colorless liquid;
HRMS (ESI-TOF) m/z: [M + H]+ calcd for C32H39O5S
1
535.2518, found 535.2519; H NMR (400 MHz, CDCl3): δ
7.72 (d, J = 8.4 Hz, 2H), 7.56-7.54 (m, 2H), 7.41-7.37 (m, 1H),
7.24-7.22 (m, 4H), 6.51 (d, J = 8.4 Hz, 1H), 6.45 (dd, J = 2.0,
8.4 Hz, 1H), 6.36 (s, 1H), 5.75 (d, J = 11.2 Hz, 1H), 3.70 (s,
3H), 3.60 (dd, J = 4.8, 11.2 Hz, 1H), 3.51 (br s, 3H), 2.89-2.83
(m, 1H), 2.44-2.37 (m, 1H), 2.10-2.01 (m, 1H), 1.89-1.54 (m,
5H), 1.37-1.24 (m, 1H), 1.16 (d, J = 7.2 Hz, 6H), 0.98-0.87 (m,
2H), 0.85-0.69 (m, 1H); 13C{1H} NMR (100 MHz, CDCl3): δ
192.6, 155.7, 147.7, 147.6, 137.6, 135.6, 133.0, 129.9 (2x),
129.3, 128.22 (2x), 128.15 (2x), 126.9 (2x), 122.3, 113.0, 110.2,
70.8, 55.5, 55.4, 50.8, 38.6, 34.1, 32.3, 27.4, 26.6, 26.2 (2x),
23.5, 23.4.
3-Cyclohexyl-3-(3,4-dimethoxyphenyl)-2-methanesulfonyl-1-
phenylpropan-1-one (3y). 3y was synthesized according to
general synthetic procedure from 4af (346 mg, 1.0 mmol) and
cC6H11MgBr (2 mL, 1.0 M in THF, 2.0 mmol). Yield = 78%
(336 mg); Colorless liquid; HRMS (ESI-TOF) m/z: [M + H]+
1
calcd for C24H31O5S 431.1892, found 431.1893; H NMR (400
MHz, CDCl3): δ 7.80-7.78 (m, 2H), 7.55-7.51 (m, 2H), 7.42-
7.38 (m, 1H), 6.61-6.56 (m, 2H), 6.45 (s, 1H), 5.51 (d, J = 10.4
Hz, 1H), 3.76 (s, 3H), 3.58 (s, 3H), 3.49 (dd, J = 4.8, 10.4 Hz,
1H), 2.94 (s, 3H), 2.17-2.10 (m, 1H), 1.94-1.90 (m, 1H), 1.86-
1.48 (m, 5H), 1.28-1.23 (m, 2H), 0.95-0.79 (m, 2H); 13C{1H}
NMR (100 MHz, CDCl3): δ 194.2, 148.0, 137.9, 133.6, 128.7
(2x), 128.6, 128.4 (3x), 122.7, 112.9, 110.3, 69.6, 55.63, 55.57,
51.6, 38.8, 38.5, 32.3, 28.0, 26.4, 26.11, 26.07.
2-(4-n-Butylbenzenesulfonyl)-3-cyclohexyl-3-(3,4-
dimethoxyphenyl)-1-phenylpropan-1-one (3ac). 3ac was syn-
thesized according to general synthetic procedure from 4aq
(464 mg, 1.0 mmol) and cC6H11MgBr (2 mL, 1.0 M in THF,
2.0 mmol). Yield = 82% (450 mg); Colorless liquid; HRMS
(ESI-TOF) m/z: [M + H]+ calcd for C33H41O5S 549.2675, found
1
549.2677; H NMR (400 MHz, CDCl3): δ 7.72 (d, J = 8.4 Hz,
3-Cyclohexyl-3-(3,4-dimethoxyphenyl)-2-(4-
2H), 7.58-7.55 (m, 2H), 7.43-7.39 (m, 1H), 7.28-7.24 (m, 2H),
7.21 (d, J = 8.4 Hz, 2H), 6.51 (d, J = 8.4 Hz, 1H), 6.44 (dd, J =
2.0, 8.4 Hz, 1H), 6.34 (s, 1H), 5.75 (d, J = 11.6 Hz, 1H), 3.71
(s, 3H), 3.59 (dd, J = 4.8, 11.6 Hz, 1H), 3.51 (br s, 3H), 2.61-
methoxybenzenesulfonyl)-1-phenylpropan-1-one (3z). 3z was
synthesized according to general synthetic procedure from 4ac
(438 mg, 1.0 mmol) and cC6H11MgBr (2 mL, 1.0 M in THF,
2.0 mmol). Yield = 74% (386 mg); Colorless liquid; HRMS
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2.57 (m, 2H), 2.45-2.39 (m, 1H), 2.10-2.01 (m, 1H), 1.82-1.50
(2x), 125.9, 124.7, 73.5, 44.5, 41.6, 30.7, 27.6, 25.14, 25.11,
21.5.
(m, 6H), 1.47-1.20 (m, 4H), 0.89 (d, J = 7.2 Hz, 3H), 0.92-0.85
(m, 2H), 0.79-0.72 (m, 1H); 13C{1H} NMR (100 MHz, CDCl3):
δ 192.7, 150.0, 155.7, 147.6, 137.7, 135.5, 133.1, 129.8 (2x),
129.3, 128.8 (2x), 128.3 (2x), 128.2 (2x), 122.3, 113.1, 110.2,
70.6, 55.6, 55.5, 50.9, 38.7, 35.5, 33.0, 32.3, 27.4, 26.7, 26.30,
26.28, 22.1, 13.8.
4-Methyl-1-phenyl-3-thiophen-2-yl-2-(toluene-4-
sulfonyl)pentan-1-one (3ag). 3ag was synthesized according to
general synthetic procedure from 4r (368 mg, 1.0 mmol) and i-
PrMgBr (2 mL, 1.0 M in THF, 2.0 mmol). Yield = 80% (330
o
mg); Colorless solid; mp = 162-164 C (recrystallized from
3-(4-Fluorophenyl)-1,3-diphenyl-2-(toluene-4-
hexanes and EtOAc); HRMS (ESI-TOF) m/z: [M + H]+ calcd
9
1
sulfonyl)propan-1-one (3ad). 3ad was synthesized according to
general synthetic procedure from 4f (362 mg, 1.0 mmol) and 4-
FC6H4MgBr (2 mL, 1.0 M in THF, 2.0 mmol). Rotamer; Yield
for C23H24O3S2 413.1245, found 413.1246; H NMR (400 MHz,
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16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
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34
35
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38
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41
42
43
44
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48
49
50
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52
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56
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58
59
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CDCl3): δ 7.64 (d, J = 8.4 Hz, 2H), 7.57-7.55 (m, 2H), 7.44-
7.40 (m, 1H), 7.31-7.24 (m, 2H), 7.17 (d, J = 8.0 Hz, 2H), 6.93
(d, J = 5.2 Hz, 1H), 6.67 (dd, J = 3.6, 5.2 Hz, 1H), 6.61 (dd, J =
1.2, 3.6 Hz, 1H), 5.58 (d, J = 11.2 Hz, 1H), 3.97 (dd, J = 3.6,
11.2 Hz, 1H), 2.90-2.82 (m, 1H), 2.33 (s, 3H), 1.13 (d, J = 6.4
Hz, 3H), 0.84 (d, J = 6.8 Jz, 3H); 13C{1H} NMR (100 MHz,
CDCl3): δ 192.3, 145.2, 138.1, 137.3, 134.8, 133.1, 129.8 (2x),
129.4 (2x), 128.3 (2x), 128.1 (2x), 128.0, 126.0, 124.3, 72.0,
46.8, 28.2, 21.6, 21.5, 16.7.
o
= 74% (339 mg); Colorless solid; mp = 246-250 C (recrystal-
lized from hexanes and EtOAc); HRMS (ESI-TOF) m/z: [M +
1
H]+ calcd for C28H24FO3S 459.1430, found 459.1432; H NMR
(400 MHz, CDCl3): δ 7.78-7.74 (m, 2H), 7.52-7.47 (m, 1H),
7.40-7.24 (m, 6H), 7.19-7.93 (m, 7H), 6.87-6.83 (m, 1H), 6.69-
6.64 (m, 1H), 6.03 (d, J = 12.0 Hz, 1H), 4.79 (t, J = 12.0 Hz,
1H), 2.35 (d, J = 2.8 Hz, 3H); 13C{1H} NMR (100 MHz,
CDCl3): δ 192.3 (1/2C), 192.1 (1/2C), 161.9 (d, J = 244.8 Hz,
1/2C), 161.44 (d, J = 244.8 Hz, 1/2C), 145.0 (1/2C), 144.9
(1/2C), 140.4 (1/2C), 138.9 (1/2C), 137.7 (1/2C), 136.5 (1/2C),
135.3 (1/2C), 135.1 (1/2C), 133.60 (1/2C), 133.55 (1/2C),
133.48 (1/2C), 133.45 (1/2C), 130.1 (J = 8.4 Hz, 1C), 129.4
(1C), 129.31 (1C), 129.28 (2C), 129.27 (1C), 129.2 (1/2C),
128.9 (1/2C), 128.8 (1/2C), 128.7 (1/2C), 128.60 (1C), 128.56
(1C), 128.5 (1C), 128.4 (2C), 127.6 (1C), 127.3 (1/2C), 127.0
(1/2C), 115.6 (d, J = 21.3 Hz, 1C), 115.4 (d, J = 19.7 Hz, 1C),
73.1 (1C), 51.2 (1/2C), 51.1 (s, 1/2C), 21.6 (1C).
3-(1-Benzyl-1H-pyrrol-2-yl)-3-cyclohexyl-1-phenyl-2-
(toluene-4-sulfonyl)propan-1-one (3ah). 3ah was synthesized
according to general synthetic procedure from 4aj (441 mg, 1.0
mmol) and cC6H11MgBr (2 mL, 1.0 M in THF, 2.0 mmol).
Yield = 80% (420 mg); Colorless liquid; HRMS (ESI-TOF)
m/z: [M + H]+ calcd for C33H36NO3S 526.2416, found 526.2418;
1H NMR (400 MHz, CDCl3): δ 8.01-7.99 (m, 2H), 7.63-7.59
(m, 1H), 7.53-7.49 (m, 2H), 7.38-7.28 (m, 5H), 7.21 (d, J = 8.4
Hz, 2H), 7.08 (d, J = 8.0 Hz, 2H), 6.42 (dd, J = 1.6, 2.8 Hz,
1H), 5.82 (t, J = 3.2 Hz, 1H), 5.59-5.55 (m, 2H), 5.22 (d, J =
15.2 Hz, 1H), 5.16 (d, J = 15.2 Hz, 1H), 4.08 (dd, J = 4.0, 11.2
Hz, 1H), 2.34 (s, 3H), 1.60-1.42 (m, 3H), 1.41-1.25 (m, 4H),
1.02-0.64 (m, 3H), 0.50-0.40 (m, 1H); 13C{1H} NMR (100
MHz, CDCl3): δ 192.9, 144.0, 137.7, 137.6, 137.5, 133.7,
129.2 (2x), 128.9 (2x), 128.59 (4x), 128.55 (2x), 128.1 (2x),
128.0, 127.6, 120.4, 109.3, 107.2, 73.9, 50.4, 41.3, 41.2, 31.2,
28.0, 26.2, 26.1, 25.7, 21.5.
3-Cyclohexyl-1-phenyl-3-thiophen-2-yl-2-(toluene-4-
sulfonyl)propan-1-one (3ae). 3ae was synthesized according to
general synthetic procedure from 4r (368 mg, 1.0 mmol) and
cC6H11MgBr (2 mL, 1.0 M in THF, 2.0 mmol). Yield = 75%
o
(339 mg); Colorless solid; mp = 168-170 C (recrystallized
from hexanes and EtOAc); HRMS (ESI-TOF) m/z: [M + H]+
calcd for C26H29O3S2 453.1558, found 453.1557; 1H NMR (400
MHz, CDCl3): δ 7.65 (d, J = 8.4 Hz, 2H), 7.58-7.55 (m, 2H),
7.44-7.40 (m, 1H), 7.28-7.24 (m, 2H), 7.18 (d, J = 8.0 Hz, 2H),
6.92 (d, J = 5.2 Hz, 1H), 6.66 (dd, J = 4.0, 5.2 Hz, 1H), 6.59
(dd, J = 0.8, 3.2 Hz, 1H), 5.66 (d, J = 11.2 Hz, 1H), 3.96 (dd, J
= 3.6, 11.2 Hz, 1H), 2.45-2.37 (m, 1H), 2.33 (s, 3H), 2.07-2.04
(m, 1H), 1.81-1.77 (m, 1H), 1.70-1.61 (m, 2H), 1.51-1.42 (m,
1H), 1.39-1.13 (m, 3H), 1.03-0.94 (m, 1H), 0.89-0.80 (m, 1H);
13C{1H} NMR (100 MHz, CDCl3): δ 192.3, 145.1, 139.1, 137.3,
135.0, 133.0, 129.8 (2x), 129.4 (2x), 128.3 (2x), 128.1 (2x),
127.7, 126.0, 124.2, 71.1, 46.6, 38.5, 32.2, 27.4, 26.6, 26.24,
26.17, 21.5.
3-Cyclohexyl-1-phenyl-3-pyridin-2-yl-2-(toluene-4-
sulfonyl)propan-1-one (3ai). 3ai was synthesized according to
general synthetic procedure from 4al (363 mg, 1.0 mmol) and
cC6H11MgBr (2 mL, 1.0 M in THF, 2.0 mmol). Yield = 82%
(367 mg); Colorless liquid; HRMS (ESI-TOF) m/z: [M + H]+
1
calcd for C27H30NO3S 448.1946, found 448.1953; H NMR
(400 MHz, CDCl3): δ 8.10 (ddd, J = 0.8, 1.6, 8.4 Hz, 1H),
7.70-7.67 (m, 2H), 7.64 (d, J = 8.0 Hz, 2H), 7.45-7.38 (m, 2H),
7.30-7.24 (m, 2H), 7.15 (d, J = 8.4 Hz, 2H), 7.00 (d, J = 7.6 Hz,
1H), 6.90 (ddd, J = 1.2, 5.2, 7.6 Hz, 1H), 6.20 (d, J = 10.8 Hz,
1H), 3.82 (dd, J = 3.2, 10.8 Hz, 1H), 2.57-2.51 (m, 1H), 2.33 (s,
3H), 2.09-2.06 (m, 1H), 1.88-1.58 (m, 3H), 1.44-1.13 (m, 3H),
1.01-0.80 (m, 2H), 0.75-0.64 (m, 1H); 13C{1H} NMR (100
MHz, CDCl3): δ 194.3, 158.1, 148.0, 144.9, 138.0, 135.5,
135.4, 132.6, 129.6 (2x), 129.3 (2x), 128.7 (2x), 127.9 (2x),
125.2, 121.6, 70.4, 52.1, 38.5, 32.6, 27.3, 26.8, 26.33, 26.26,
21.5.
3-Cyclopentyl-1-phenyl-3-thiophen-2-yl-2-(toluene-4-
sulfonyl)-propan-1-one (3af). 3af was synthesized according to
general synthetic procedure from 4r (368 mg, 1.0 mmol) and
cC5H9MgBr (2 mL, 1.0 M in THF, 2.0 mmol). Yield = 78%
o
(342 mg); Colorless solid; mp = 156-158 C (recrystallized
from hexanes and EtOAc); HRMS (ESI-TOF) m/z: [M + H]+
calcd for C25H27O3S2 439.1402, found 439.1403; 1H NMR (400
MHz, CDCl3): δ 7.62-7.57 (m, 4H), 7.47-7.43 (m, 1H), 7.31-
7.27 (m, 2H), 7.14 (d, J = 8.0 Hz, 2H), 6.95 (dd, J = 1.2, 4.4 Hz,
1H), 6.71-6.67 (m, 2H), 5.52 (d, J = 10.0 Hz, 1H), 4.17-4.13
(m, 1H), 2.84-2.78 (m, 1H), 2.32 (s, 3H), 1.95-1.89 (m, 1H),
1.72-1.65 (m, 2H), 1.55-1.37 (m, 4H), 1.19-1.09 (m, 1H);
13C{1H} NMR (100 MHz, CDCl3): δ 192.4, 145.0, 139.6, 137.3,
134.9, 133.2, 129.7 (2x), 129.4 (2x), 128.41, 128.39 (2x), 128.2
3-Cyclohexyl-3-furan-2-yl-1-phenyl-2-(toluene-4-
sulfonyl)propan-1-one (3aj). 3aj was synthesized according to
general synthetic procedure from 4am (352 mg, 1.0 mmol) and
cC6H11MgBr (2 mL, 1.0 M in THF, 2.0 mmol). Yield = 80%
o
(349 mg); Colorless solid; mp = 108-109 C (recrystallized
from hexanes and EtOAc); HRMS (ESI-TOF) m/z: [M + H]+
1
calcd for C26H29O4S 437.1787, found 437.1786; H NMR (400
MHz, CDCl3): δ 7.68-7.61 (m, 3H), 7.48-7.43 (m, 1H), 7.32-
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The Journal of Organic Chemistry
7.28 (m, 2H), 7.20 (d, J = 8.0 Hz, 2H), 6.96 (d, J = 1.2 Hz, 1H),
mmol) and cC5H9MgBr (2 mL, 1.0 M in THF, 2.0 mmol).
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6.04 (dd, J = 2.0, 3.2 Hz, 1H), 5.86 (dd, J = 0.8, 3.2 Hz, 1H),
5.75 (d, J = 10.8 Hz, 1H), 3.67 (dd, J = 3.2, 10.8 Hz, 1H), 2.40-
2.33 (m, 1H), 2.35 (s, 3H), 2.10-2.04 (m, 1H), 1.76-1.55 (m,
4H), 1.43-1.23 (m, 3H), 1.04-0.83 (m, 3H); 13C{1H} NMR (100
MHz, CDCl3): δ 192.8, 151.4, 145.2, 141.2, 137.0, 134.9,
133.1, 129.8 (2x), 129.4 (2x), 128.3 (2x), 128.2 (2x), 110.1,
109.1, 69.1, 45.1, 38.4, 32.1, 27.9, 26.5, 26.2 (2x), 21.6.
Yield = 72% (383 mg); Colorless liquid; HRMS (ESI-TOF)
m/z: [M + H]+ calcd for C32H37O5S 533.2362, found 533.2366;
1H NMR (400 MHz, CDCl3): δ 7.70 (d, J = 8.4 Hz, 2H), 7.55-
7.53 (m, 2H), 7.45-7.40 (m, 1H), 7.30-7.26 (m, 2H), 7.22 (d, J
= 8.4 Hz, 2H), 6.54 (d, J = 8.8 Hz, 1H), 6.29 (d, J = 8.8 Hz,
1H), 5.83-5.73 (m, 1H), 5.61 (d, J = 10.4 Hz, 1H), 4.95-4.90
(m, 2H), 4.02 (dd, J = 5.2, 10.4 Hz, 1H), 3.70 (s, 3H), 3.64 (s,
3H), 3.41 (dd, J = 8.0, 15.2 Hz, 1H), 3.34-3.28 (m, 1H), 2.81-
2.74 (m, 1H), 2.35 (s, 3H), 1.93-1.87 (m, 1H), 1.75-1.68 (m,
1H), 1.54-1.41 (m, 4H), 1.35-1.27 (m, 1H), 0.89-0.82 (m, 1H);
13C{1H} NMR (100 MHz, CDCl3): δ 192.9, 151.2, 147.4, 145.0,
138.1, 136.8, 134.8, 134.2, 132.8, 129.9 (2x), 129.3 (2x), 129.0,
128.2 (2x), 128.1 (2x), 124.2, 115.0, 109.0, 73.8, 60.5, 55.3,
42.5, 41.5, 31.2, 30.3, 27.4, 24.2, 24.0, 21.5.
3
4
5
6
7
8
9
2-Benzenesulfonyl-3-cyclohexyl-1-phenyl-3-thiophen-2-
ylpropan-1-one (3ak). 3ak was synthesized according to gen-
eral synthetic procedure from 4ak (354 mg, 1.0 mmol) and
cC6H11MgBr (2 mL, 1.0 M in THF, 2.0 mmol). Yield = 86%
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
o
(377 mg); Colorless solid; mp = 230-231 C (recrystallized
from hexanes and EtOAc); HRMS (ESI-TOF) m/z: [M + H]+
calcd for C25H27O3S2 439.1402, found 439.1405; 1H NMR (400
MHz, CDCl3): δ 7.79 (d, J = 7.6 Hz, 2H), 7.56 (d, J = 7.6 Hz,
2H), 7.51-7.47 (m, 1H), 7.43-7.37 (m, 3H), 7.27-7.24 (m, 2H),
6.92 (d, J = 8.8 Hz, 1H), 6.66 (dd, J = 3.2, 8.4 Hz, 1H), 6.59 (d,
J = 7.6 Hz, 1H), 5.69 (d, J = 10.8 Hz, 1H), 4.00 (dd, J = 3.6,
10.8 Hz, 1H), 2.44-2.37 (m, 1H), 2.06-2.03 (m, 1H), 1.80-1.77
(m, 1H), 1.70-1.52 (m, 3H), 1.42-1.29 (m, 2H), 1.24-1.14 (m,
1H), 1.03-0.94 (m, 1H), 0.90-0.79 (m, 1H); 13C{1H} NMR (100
MHz, CDCl3): δ 192.2, 139.0, 138.1, 137.2, 134.0, 133.2,
129.7 (2x), 128.8 (2x), 128.2 (4x), 127.8, 126.0, 124.3, 71.0,
46.7, 38.6, 32.2, 27.4, 26.6, 26.23, 26.17.
General synthetic procedure of compounds 3ao-3as is as fol-
lows: NaBH4 (38 mg, 1.0 mmol) was added to a solution of 4a,
4b, 4e, 4w and 4x (0.3 mmol) in THF and MeOH (v/v =1/1, 10
o
o
mL) at 25 C. The reaction mixture was stirred at 25 C for 30
o
min. The reaction mixture was cooled to 25 C and the solvent
was concentrated. The residue was diluted with water (10 mL)
and the mixture was extracted with CH2Cl2 (3 x 20 mL). The
combined organic layers were washed with brine, dried, fil-
tered and evaporated to afford crude product under reduced
pressure. Without further purification, PCC (216 mg, 1.0 mmol)
was added to a solution of the resulting crude products in a
3-Benzo[b]furan-2-yl-3-cyclohexyl-1-phenyl-2-(toluene-4-
sulfonyl)propan-1-one (3al). 3al was synthesized according to
general synthetic procedure from 4an (402 mg, 1.0 mmol) and
cC6H11MgBr (2 mL, 1.0 M in THF, 2.0 mmol). Yield = 83%
o
CH2Cl2 (10 mL) at 25 C. Then, Celite (200 mg) was added to
o
the reaction mixture at 25 C. The reaction mixture was stirred
o
at 25 C for 3 h. The reaction mixture was filtrated, and the
o
combined organic layers were washed with brine (2 x 10 mL),
dried (MgSO4), filtered and evaporated to afford crude product
mixture under reduced pressure. The remaining mixture was
separated by column chromatography (silica gel, hex-
anes/EtOAc = 8/1~4/1 as eluent) affording 3ao-3a.
(404 mg); Colorless solid; mp = 203-204 C (recrystallized
from hexanes and EtOAc); HRMS (ESI-TOF) m/z: [M + H]+
1
calcd for C30H31O4S 487.1943, found 487.1945; H NMR (400
MHz, CDCl3): δ 7.68 (d, J = 8.4 Hz, 2H), 7.62 (d, J = 7.6 Hz,
2H), 7.43-7.19 (m, 6H), 7.07-7.04 (m, 3H), 6.30 (s, 1H), 5.89
(d, J = 10.8 Hz, 1H), 3.82 (dd, J = 3.2, 10.8 Hz, 1H), 2.52-2.42
(m, 1H), 2.35 (s, 3H), 2.17-2.13 (m, 1H), 1.76-1.61 (m, 4H),
1.45-1.28 (m, 3H), 1.08-0.92 (m, 2H); 13C{1H} NMR (100
MHz, CDCl3): δ 192.7, 154.4, 154.0, 145.3, 137.0, 134.8,
133.1, 129.8 (2x), 129.4 (2x), 128.3 (2x), 128.1 (2x), 128.0,
123.5, 122.6, 120.6, 110.5, 106.0, 68.9, 45.6, 38.4, 32.2, 28.1,
26.5, 26.0, 26.1, 21.5.
3-(3,4-Dimethoxyphenyl)-1-phenyl-2-(toluene-4-
sulfonyl)propan-1-one (3ao). 3ao was synthesized according to
general synthetic procedure from 4a (127 mg, 0.3 mmol). Yield
o
= 90% (114 mg); Colorless solid; mp = 125-126 C (recrystal-
lized from hexanes and EtOAc); HRMS (ESI-TOF) m/z: [M +
1
H]+ Calcd for C24H25O5S 425.1423; Found 425.1430; H NMR
(400 MHz, CDCl3): δ 7.73-7.71 (m, 2H), 7.67 (d, J = 8.4 Hz,
2H), 7.47-7.43 (m, 1H), 7.32-7.26 (m, 4H), 6.60 (d, J = 1.2 Hz,
2H), 6.55 (br s, 1H), 5.32 (dd, J = 2.8, 11.2 Hz, 1H), 3.69 (s,
3H), 3.66 (s, 3H), 3.41 (dd, J = 2.8, 13.2 Hz, 1H), 3.27 (dd, J =
11.2, 13.2 Hz, 1H), 2.38 (s, 3H); 13C{1H} NMR (100 MHz,
CDCl3): δ 192.4, 148.7, 147.7, 145.3, 137.1, 133.6, 133.2,
129.6 (2x), 129.4 (2x), 128.5 (2x), 128.4 (2x), 128.1, 120.8,
111.8, 111.2, 71.3, 55.5 (2x), 35.5, 21.5.
3-Benzo[b]thiophen-2-yl-3-cyclohexyl-1-phenyl-2-(toluene-
4-sulfonyl)propan-1-one (3am). 3am was synthesized accord-
ing to general synthetic procedure from 4ao (418 mg, 1.0 mmol)
and cC6H11MgBr (2 mL, 1.0 M in THF, 2.0 mmol). Yield =
o
80% (402 mg); Colorless solid; mp = 225-226 C (recrystal-
lized from hexanes and EtOAc); HRMS (ESI-TOF) m/z: [M +
1
H]+ calcd for C30H31O3S2 503.1715, found 503.1718; H NMR
(400 MHz, CDCl3): δ 7.60-7.52 (m, 5H), 7.46 (d, J = 7.2 Hz,
1H), 7.36 (t, J = 7.6 Hz, 1H), 7.22-7.09 (m, 6H), 6.81 (s, 1H),
5.72 (d, J = 11.2 Hz, 1H), 3.98 (dd, J = 3.6, 10.8 Hz, 1H), 2.46-
2.41 (m, 1H), 2.28 (s, 3H), 2.07-2.04 (m, 1H), 1.77-1.74 (m,
1H), 1.66-1.56 (m, 4H), 1.35-1.18 (m, 3H), 0.96-0.88 (m, 1H);
13C{1H} NMR (100 MHz, CDCl3): δ 191.9, 145.2, 140.6, 139.3,
138.9, 137.2, 134.9, 133.1, 129.8 (2x), 129.4 (2x), 128.5 (2x),
128.2 (2x), 124.6, 124.0, 123.8, 123.0, 121.7, 70.8, 47.3, 38.6,
32.3, 27.7, 26.6, 26.23, 26.21, 21.5.
3-Benzo[1,3]dioxol-5-yl-1-phenyl-2-(toluene-4-
sulfonyl)propan-1-one (3ap). 3ap was synthesized according to
general synthetic procedure from 4b (122 mg, 0.3 mmol).
o
Yield = 86% (105 mg); Colorless solid; mp = 123-125 C (re-
crystallized from hexanes and EtOAc); HRMS (ESI-TOF) m/z:
1
[M + H]+ Calcd for C23H21O5S 409.1110; Found 409.1118; H
NMR (400 MHz, CDCl3): δ 7.73-7.70 (m, 2H), 7.63 (d, J = 8.4
Hz, 2H), 7.48-7.44 (m, 1H), 7.33-7.25 (m, 4H), 6.54-6.48 (m,
3H), 5.77 (d, J = 1.2 Hz, 1H), 5.76 (d, J = 1.2 Hz, 1H), 5.22
(dd, J = 3.2, 11.6 Hz, 1H), 3.33 (dd, J = 3.2, 13.6 Hz, 1H), 3.22
(dd, J = 11.6, 13.6 Hz, 1H), 2.38 (s, 3H); 13C{1H} NMR (100
MHz, CDCl3): δ 192.1, 147.7, 146.5, 145.5, 137.2, 133.7,
3-(2-Allyl-3,4-dimethoxyphenyl)-3-cyclopentyl-1-phenyl-2-
(toluene-4-sulfonyl)propan-1-one (3an). 3an was synthesized
according to general synthetic procedure from 4p (362 mg, 1.0
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133.3, 129.7 (2x), 129.5 (2x), 129.4, 128.7 (2x), 128.5 (2x),
122.0, 109.2, 108.4, 100.9, 71.5, 33.6, 21.6.
1-Cyclohexyl-5,6-dimethoxy-3-phenyl-2-(toluene-4-
sulfonyl)-1H-indene (1a). 1a was synthesized according to
general synthetic procedure from 3g (101 mg, 0.2 mmol). Yield
1-Phenyl-2-(toluene-4-sulfonyl)-3-(3,4,5-
o
= 90% (88 mg); Colorless solid; mp = 178-181 C (recrystal-
trimethoxyphenyl)propan-1-one (3aq). 3aq was synthesized
according to general synthetic procedure from 4e (136 mg, 0.3
mmol). Yield = 90% (123 mg); Colorless solid; mp = 153-155
oC (recrystallized from hexanes and EtOAc); HRMS (ESI-TOF)
m/z: [M + H]+ Calcd for C25H27O6S 455.1528; Found 455.1536;
1H NMR (400 MHz, CDCl3): δ 7.76-7.73 (m, 2H), 7.67 (d, J =
8.0 Hz, 2H), 7.49-7.45 (m, 1H), 7.34-7.28 (m, 4H), 6.24 (s, 2H),
5.35 (dd, J = 3.2, 11.6 Hz, 1H), 3.67 (s, 3H), 3.63 (s, 6H), 3.42
(dd, J = 2.8, 13.2 Hz, 1H), 3.26 (dd, J = 11.6, 13.2 Hz, 1H),
2.39 (s, 3H); 13C{1H} NMR (100 MHz, CDCl3): δ 192.5, 153.0
(2x), 145.4, 137.1, 136.6, 133.7, 133.2, 131.3, 129.7 (2x),
129.5 (2x), 128.6 (2x), 128.4 (2x), 105.7 (2x), 71.1, 60.5, 55.8
(2x), 34.3, 21.5.
lized from hexanes and EtOAc); HRMS (ESI-TOF) m/z: [M +
H]+ calcd for C30H33O4S 489.2100, found 489.2101; H NMR
1
(400 MHz, CDCl3): δ 7.41-7.33 (m, 5H), 7.31 (d, J = 8.4 Hz,
2H), 7.08 (s, 1H), 7.00 (d, J = 8.4 Hz, 2H), 6.49 (s, 1H), 4.06 (d,
J = 3.2 Hz, 1H), 3.95 (s, 3H), 3.71 (s, 3H), 2.76-2.69 (m, 1H),
2.31 (s, 3H), 2.04-2.03 (m, 1H), 1.86-1.83 (m, 1H), 1.74-1.64
(m, 3H), 1.54-1.39 (m, 2H), 1.23-0.97 (m, 2H), 0.49-0.38 (m,
1H); 13C{1H} NMR (100 MHz, CDCl3): δ 152.4, 149.7, 148.8,
143.2, 141.4, 139.1, 139.0, 136.4, 132.5, 128.8 (2x), 128.4 (2x),
127.9 (3x), 127.5 (2x), 108.1, 105.4, 57.4, 56.3, 56.0, 39.7,
32.5, 27.2, 26.5, 26.1 (2x), 21.4. Single-crystal X-Ray diagram:
crystal of 1a was grown by slow diffusion of EtOAc into a
solution of 1a in CH2Cl2 to yield colorless prisms. The com-
pound crystallizes in the monoclinic crystal system, space
group P 21/n, a = 12.0497(17) Å , b = 14.261(2) Å , c = 15.114(2)
Å , V = 2549.5(7) Å 3, Z = 4, dcalcd = 1.273 g/cm3, F(000) = 1040,
2θ range 1.981~26.451o, R indices (all data) R1 = 0.0544, wR2
= 0.0985.
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13
14
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16
17
18
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20
21
22
23
24
25
26
27
28
29
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31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
3-(3,4-Dimethoxyphenyl)-2-(toluene-4-sulfonyl)-1-(4-
trifluoromethylphenyl)propan-1-one (3ar). 3ar was synthe-
sized according to general synthetic procedure from 4w (147
mg, 0.3 mmol). Yield = 84% (124 mg); Colorless solid; mp =
o
120-122 C (recrystallized from hexanes and EtOAc); HRMS
(ESI-TOF) m/z: [M + H]+ Calcd for C25H24F3O5S 493.1297;
1
5-Cyclohexyl-7-phenyl-6-(toluene-4-sulfonyl)-5H-
Found 493.1299; H NMR (400 MHz, CDCl3): δ 7.82 (d, J =
indeno[5,6-d][1,3]dioxole (1b). 1b was synthesized according
to general synthetic procedure from 3h (98 mg, 0.2 mmol).
Yield = 86% (81 mg); Colorless liquid; HRMS (ESI-TOF) m/z:
8.0 Hz, 2H), 7.67 (d, J = 8.4 Hz, 2H), 7.53 (d, J = 8.4 Hz, 2H),
7.27 (d, J = 8.0 Hz, 2H), 6.59-6.58 (m, 3H), 5.40 (dd, J = 3.2,
11.6 Hz, 1H), 3.67 (s, 3H), 3.66 (s, 3H), 3.44 (dd, J = 3.2, 13.2
Hz, 1H), 3.27 (dd, J = 12.0, 13.2 Hz, 1H), 2.35 (s, 3H); 13C{1H}
NMR (100 MHz, CDCl3): δ 191.8, 148.7, 147.8, 145.6, 139.6,
134.4 (q, J = 32.6 Hz), 133.0, 129.53 (2x), 129.49 (2x), 128.8
(2x), 127.7, 125.3 (q, J = 3.8 Hz, 2x), 123.1 (q, J = 271.4 Hz),
120.7, 111.8, 111.1, 71.6, 55.5, 55.4, 33.3, 21.3.
[M + H]+ calcd for C29H29O4S 473.1787, found 473.1788; H
1
NMR (400 MHz, CDCl3): δ 7.39-7.30 (m, 3H), 7.31 (d, J = 8.4
Hz, 2H), 7.04 (s, 1H), 7.01 (d, J = 8.4 Hz, 2H), 6.45 (s, 1H),
5.97 (d, J = 1.2 Hz, 1H), 5.96 (d, J = 1.2 Hz, 1H), 4.02 (d, J =
3.2 Hz, 1H), 2.74-2.67 (m, 1H), 2.31 (s, 3H), 2.04-2.03 (m, 1H),
1.86-1.83 (m, 1H), 1.74-1.64 (m, 3H), 1.54-1.39 (m, 3H), 1.20-
0.99 (m, 3H), 0.51-0.40 (m, 1H); 13C{1H} NMR (100 MHz,
CDCl3): δ 152.2, 148.4, 147.2, 143.2, 141.6, 140.6, 139.1,
137.8, 132.4, 128.9 (2x), 128.5 (2x), 127.9 (2x), 127.5 (3x),
105.8, 103.2, 101.5, 57.2, 39.8, 32.6, 27.2, 26.4, 26.13, 26.06,
21.5.
3-(3,4-Dimethoxyphenyl)-1-(4-nitrophenyl)-2-(toluene-4-
sulfonyl)propan-1-one (3as). 3as was synthesized according to
general synthetic procedure from 4x (140 mg, 0.3 mmol). Yield
o
= 90% (127 mg); Colorless solid; mp = 148-150 C (recrystal-
lized from hexanes and EtOAc); HRMS (ESI-TOF) m/z: [M +
H]+ Calcd for C24H24NO7S 470.1274; Found 470.1274; 1H
NMR (400 MHz, CDCl3): δ 8.13 (d, J = 8.4 Hz, 2H), 7.88 (d, J
= 8.8 Hz, 2H), 7.67 (d, J = 8.8 Hz, 2H), 7.33 (d, J = 8.0 Hz,
2H), 6.61-6.55 (m, 3H), 5.36 (dd, J = 2.8, 11.6 Hz, 1H), 3.69 (s,
3H), 3.68 (s, 3H), 3.41 (dd, J = 2.8, 13.2 Hz, 1H), 3.22 (dd, J =
11.6, 13.2 Hz, 1H), 2.42 (s, 3H); 13C{1H} NMR (100 MHz,
CDCl3): δ 191.7, 150.2, 148.9, 147.9, 145.9, 141.4, 132.8,
129.7 (4x), 129.6 (2x), 127.5, 123.6 (2x), 120.8, 111.9, 111.2,
72.1, 55.6, 55.5, 33.7, 21.5.
1-Cyclohexyl-4,5,6-trimethoxy-3-phenyl-2-(toluene-4-
sulfonyl)-1H-indene (1c). 1c was synthesized according to gen-
eral synthetic procedure from 3i (107 mg, 0.2 mmol). Yield =
90% (93 mg); Colorless solid; mp = 150-152 oC (recrystallized
from hexanes and EtOAc); HRMS (ESI-TOF) m/z: [M + H]+
1
calcd for C31H35O5S 519.2205, found 519.2204; H NMR (400
MHz, CDCl3): δ 7.34-7.26 (m, 3H), 7.23 (d, J = 8.0 Hz, 2H),
7.16-7.13 (m, 1H), 6.99 (d, J = 8.0 Hz, 2H), 6.90 (d, J = 7.6 Hz,
1H), 6.87 (s, 1H), 4.08 (d, J = 2.8 Hz, 1H), 3.92 (s, 3H), 3.76 (s,
3H), 3.22 (s, 3H), 2.77-2.68 (m, 1H), 2.32 (s, 3H), 2.04-2.01
(m, 1H), 1.86-1.83 (m, 1H), 1.73-1.64 (m, 3H), 1.55-1.38 (m,
2H), 1.24-0.85 (m, 2H), 0.53-0.42 (m, 1H); 13C{1H} NMR (100
MHz, CDCl3): δ 154.3, 151.7, 150.1, 143.1, 142.6, 141.7,
141.5, 139.1, 134.0, 129.2, 128.9, 128.8 (2x), 128.4, 127.6,
127.5 (2x), 127.0, 126.9, 104.4, 60.92, 60.88, 57.6, 56.3, 40.0,
32.2, 27.2, 26.4, 26.1, 26.0, 21.4.
General synthetic procedure of skeleton 1 is as follows: A-
15 (100 mg) was added to a solution of 3 (0.2 mmol) in toluene
(10 mL) at 25 oC. The reaction mixture was stirred at reflux for
10 h under Dean-Stark distillation apparatus. The reaction mix-
ture was cooled to 25 oC. A-15 was filtered by filter paper and
the A-15 was washed with toluene (3 x 5 mL). The combined
toluene layers were concentrated. The residue was diluted with
saturated NaHCO3(aq) (10 mL) and the mixture was extracted
with EtOAc (3 x 20 mL). The combined organic layers were
washed with brine (2 x 10 mL), dried (MgSO4), filtered and
evaporated to afford crude product mixture under reduced pres-
sure. The remaining mixture was separated by column chroma-
tography (silica gel, hexanes/EtOAc = 8/1~4/1 as eluent) af-
fording 1.
5,6-Dimethoxy-1,3-diphenyl-2-(toluene-4-sulfonyl)-1H-
indene (1d). 1d was synthesized according to general synthetic
procedure from 3j (100 mg, 0.2 mmol). Yield = 89% (86 mg);
o
Colorless solid; mp = 194-196 C (recrystallized from hexanes
and EtOAc); HRMS (ESI-TOF) m/z: [M + H]+ calcd for
1
C30H27O4S 483.1630, found 483.1631; H NMR (400 MHz,
CDCl3): δ 7.50-7.47 (m, 3H), 7.39 (br s, 2H), 7.24-7.17 (m,
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The Journal of Organic Chemistry
3H), 7.05-7.03 (m, 2H), 6.88 (br s, 4H), 6.71 (s, 1H), 6.58 (s,
2.30 (s, 3H), 2.13-1.90 (m, 1H), 1.90-1.81 (m, 1H), 1.63-1.44
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3
4
5
6
7
1H), 5.13 (s, 1H), 3.79 (s, 3H), 3.75 (s, 3H), 2.28 (s, 3H);
13C{1H} NMR (100 MHz, CDCl3): δ 153.6, 150.9, 149.2,
143.00, 142.96, 142.3, 139.1, 137.4, 135.4, 132.4, 129.0,
128.78 (2x), 128.75 (2x), 128.7 (2x), 128.6 (2x), 128.1 (2x),
127.4 (2x), 127.2, 107.1, 105.4, 57.3, 56.2, 56.1, 21.4.
(m, 4H), 0.90-0.83 (m, 1H), 0.59-0.52 (m, 1H); 13C{1H} NMR
(100 MHz, CDCl3): δ 151.6, 149.6, 148.9, 143.1, 142.9, 139.1,
138.8, 136.8, 132.5, 128.8 (2x), 128.4 (2x), 127.9 (3x), 127.4
(2x), 108.2, 105.3, 56.3, 56.0, 54.1, 40.5, 30.8, 25.7, 25.6, 25.1,
21.4. Single-crystal X-Ray diagram: crystal of 1h was grown
by slow diffusion of EtOAc into a solution of 1h in CH2Cl2 to
yield colorless prisms. The compound crystallizes in the mono-
clinic crystal system, space group P 21/n, a = 11.8975(5) Å , b =
14.8380(7) Å , c = 14.1035(7) Å , V = 2480.8(2) Å 3, Z = 4, dcalcd
= 1.271 g/cm3, F(000) = 1008, 2θ range 1.996~26.405o, R indi-
ces (all data) R1 = 0.0525, wR2 = 0.1060.
1-(4-Fluorophenyl)-5,6-dimethoxy-3-phenyl-2-(toluene-4-
sulfonyl)-1H-indene (1e). 1e was synthesized according to gen-
eral synthetic procedure from 3k (104 mg, 0.2 mmol). Yield =
85% (85 mg); Colorless solid; mp = 155-156 oC (recrystallized
from hexanes and EtOAc); HRMS (ESI-TOF) m/z: [M + H]+
calcd for C30H26FO4S 501.1536, found 501.1533; 1H NMR
(400 MHz, CDCl3): δ 7.50-7.47 (m, 3H), 7.39 (br s, 2H), 7.02-
6.97 (m, 2H), 6.95-6.86 (m, 6H), 6.69 (s, 1H), 6.57 (s, 1H),
5.11 (s, 1H), 3.80 (s, 3H), 3.75 (s, 3H), 2.29 (s, 3H); 13C{1H}
NMR (100 MHz, CDCl3): δ 162.1 (d, J = 244.1 Hz), 153.6,
151.0, 149.3, 143.2, 142.8, 142.0, 139.1, 135.2, 133.1 (d, J =
3.0 Hz), 132.2, 130.3 (d, J = 8.3 Hz, 2x), 129.0, 128.82 (2x),
128.78 (2x), 128.1 (2x), 127.3 (2x), 115.4 (d, J = 21.2 Hz, 2x),
107.0, 105.5, 56.4, 56.2, 56.1, 21.4. Single-crystal X-Ray dia-
gram: crystal of 1e was grown by slow diffusion of EtOAc into
a solution of 1e in CH2Cl2 to yield colorless prisms. The com-
pound crystallizes in the monoclinic crystal system, space
group P 21/n, a = 14.241(2) Å , b = 11.0536(15) Å , c = 15.619(2)
Å , V = 2442.6(6) Å 3, Z = 4, dcalcd= 1.361 g/cm3, F(000) = 1048,
2θ range 1.834~26.922o, R indices (all data) R1 = 0.1087, wR2
= 0. 1785.
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1-Cyclohexyl-3-(4-fluorophenyl)-5,6-dimethoxy-2-(toluene-
4-sulfonyl)-1H-indene (1i). 1i was synthesized according to
general synthetic procedure 3r (105 mg, 0.2 mmol). Yield =
89% (90 mg); Colorless solid; mp = 166-167 oC (recrystallized
from hexanes and EtOAc); HRMS (ESI-TOF) m/z: [M + H]+
calcd for C30H32FO4S 507.2005, found 507.2004; 1H NMR
(400 MHz, CDCl3): δ 7.33 (d, J = 8.4 Hz, 2H), 7.15 (br s, 2H),
7.09-7.04 (m, 5H), 6.46 (s, 1H), 4.04 (d, J = 2.8 Hz, 1H), 3.95
(s, 3H), 3.72 (s, 3H), 2.75-2.68 (m, 1H), 2.33 (s, 3H), 2.04-2.01
(m, 1H), 1.86-1.83 (m, 1H), 1.73-1.64 (m, 3H), 1.55-1.38 (m,
2H), 1.24-0.96 (m, 2H), 0.48-0.38 (m, 1H); 13C{1H} NMR (100
MHz, CDCl3): δ 162.9 (d, J = 246.4 Hz), 151.4, 149.8, 148.9,
143.4, 141.9, 139.1, 139.0, 136.2, 131.0 (2x), 128.9 (2x),
128.42 (d, J = 3.0 Hz), 127.4 (2x), 115.1 (d, J = 21.3 Hz, 2x),
108.2, 105.1, 57.4, 56.3, 56.0, 39.8, 32.5, 27.2, 26.4, 26.2, 26.1,
21.4.
5,6-Dimethoxy-1-(4-methoxyphenyl)-3-phenyl-2-(toluene-4-
sulfonyl)-1H-indene (1f). 1f was synthesized according to gen-
eral synthetic procedure from 3l (106 mg, 0.2 mmol). Yield =
92% (94 mg); Colorless liquid; HRMS (ESI-TOF) m/z: [M +
1-Cyclohexyl-5,6-dimethoxy-2-(toluene-4-sulfonyl)-3-p-
tolyl-1H-indene (1j). 1j was synthesized according to general
synthetic procedure from 3s (104 mg, 0.2 mmol). Yield = 90%
(90 mg); Colorless solid; mp = 167-168 oC (recrystallized from
hexanes and EtOAc); HRMS (ESI-TOF) m/z: [M + H]+ calcd
1
H]+ calcd for C31H29O5S 513.1736, found 513.1736; H NMR
(400 MHz, CDCl3): δ 7.49-7.46 (m, 3H), 7.38 (br s, 2H), 6.98-
6.88 (m, 6H), 6.73 (d, J = 8.4 Hz, 2H), 6.71 (s, 1H), 6.56 (s,
1H), 5.09 (s, 1H), 3.81 (s, 3H), 3.80 (s, 3H), 3.74 (s, 3H), 2.28
(s, 3H); 13C{1H} NMR (100 MHz, CDCl3): δ 158.8, 153.2,
150.9, 149.1, 143.04, 142.95, 142.4, 139.2, 135.2, 132.4, 129.8
(2x), 129.0 (2x), 128.7 (3x), 128.1 (2x), 127.4 (2x), 124.4,
114.0 (2x), 107.1, 105.3, 56.6, 56.2, 56.1, 55.3, 21.4.
1
for C31H35O4S 503.2256, found 503.2254; H NMR (400 MHz,
CDCl3): δ 7.34 (d, J = 8.4 Hz, 2H), 7.15 (br s, 2H), 7.07 (s, 3H),
7.02 (d, J = 7.6 Hz, 2H), 6.52 (s, 1H), 4.02 (d, J = 2.8 Hz, 1H),
3.94 (s, 3H), 3.72 (s, 3H), 2.74-2.67 (m, 1H), 2.42 (s, 3H), 2.32
(s, 3H), 2.04-2.01 (m, 1H), 1.86-1.83 (m, 1H), 1.73-1.64 (m,
3H), 1.55-1.38 (m, 2H), 1.24-0.96 (m, 2H), 0.47-0.37 (m, 1H);
13C{1H} NMR (100 MHz, CDCl3): δ 152.7, 149.6, 148.8, 143.1,
141.1, 139.3, 139.1, 138.4, 136.6, 129.5, 129.2 (2x), 128.8 (2x),
128.6 (2x), 127.5 (2x), 108.1, 105.4, 57.3, 56.3, 56.0, 39.7,
32.5, 27.2, 26.5, 26.1 (2x), 21.44, 21.41.
1-Isopropyl-5,6-dimethoxy-3-phenyl-2-(toluene-4-sulfonyl)-
1H-indene (1g). 1g was synthesized according to general syn-
thetic procedure from 3p (93 mg, 0.2 mmol). Yield = 74% (66
mg); Colorless liquid; HRMS (ESI-TOF) m/z: [M + H]+ calcd
1
for C27H29O4S 449.1787, found 449.1788; H NMR (400 MHz,
1-Cyclohexyl-5,6-dimethoxy-3-(4-methoxyphenyl)-2-
CDCl3): δ 7.41-7.30 (m, 5H), 7.30 (d, J = 8.4 Hz, 2H), 7.09 (s,
1H), 6.99 (d, J = 8.4 Hz, 2H), 6.51 (s, 1H), 4.07 (d, J = 3.2 Hz,
1H), 3.94 (s, 3H), 3.72 (s, 3H), 3.20-3.13 (m, 1H), 2.30 (s, 3H),
1.39 (d, J = 6.8 Hz, 3H), 0.50 (d, J = 6.8 Hz, 3H); 13C{1H}
NMR (100 MHz, CDCl3): δ 152.3, 149.7, 148.8, 143.1, 141.9,
139.1, 138.4, 136.5, 132.4, 128.8 (3x), 128.5 (2x), 128.0 (2x),
127.4 (2x), 108.0, 105.4, 57.5, 56.2, 56.0, 29.2, 21.9, 21.4, 15.4.
(toluene-4-sulfonyl)-1H-indene (1k). 1k was synthesized ac-
cording to general synthetic procedure from 3t (107 mg, 0.2
mmol). Yield = 93% (96 mg); Colorless solid; mp = 184-185
oC (recrystallized from hexanes and EtOAc); HRMS (ESI-TOF)
m/z: [M + H]+ calcd for C31H35O5S 519.2205, found 519.2207;
1H NMR (400 MHz, CDCl3): δ 7.33 (d, J = 8.4 Hz, 2H), 7.15
(br s, 2H), 7.07 (s, 1H), 7.2 (d, J = 8.0 Hz, 2H), 6.89 (d, J = 8.4
Hz, 2H), 6.54 (s, 1H), 4.02 (d, J = 3.2 Hz, 1H), 3.95 (s, 3H),
3.88 (s, 3H), 3.73 (s, 3H), 2.74-2.67 (m, 1H), 2.31 (s, 3H),
2.04-2.01 (m, 1H), 1.86-1.83 (m, 1H), 1.69-1.63 (m, 3H), 1.53-
1.41 (m, 2H), 1.29-0.99 (m, 2H), 0.44-0.40 (m, 1H); 13C{1H}
NMR (100 MHz, CDCl3): δ 159.9, 152.4, 149.6, 148.8, 143.1,
141.0, 139.3, 139.1, 136.6, 130.7 (2x), 128.8 (2x), 127.4 (2x),
124.7, 113.4 (2x), 108.1, 105.4, 57.3, 56.3, 56.0, 55.3, 39.8,
32.5, 27.2, 26.5, 26.2, 26.1, 21.4.
1-Cyclopentyl-5,6-dimethoxy-3-phenyl-2-(toluene-4-
sulfonyl)-1H-indene (1h). 1h was synthesized according to
general synthetic procedure from 3q (98 mg, 0.2 mmol). Yield
o
= 86% (82 mg); Colorless solid; mp = 206-207 C (recrystal-
lized from hexanes and EtOAc); HRMS (ESI-TOF) m/z: [M +
1
H]+ calcd for C29H31O4S 475.1943, found 475.1944; H NMR
(400 MHz, CDCl3): δ 7.40-7.33 (m, 5H), 7.29 (d, J = 8.4 Hz,
2H), 7.11 (s, 1H), 6.98 (d, J = 8.0 Hz, 2H), 6.50 (s, 1H), 4.30 (d,
J = 3.6 Hz, 1H), 3.93 (s, 3H), 3.71 (s, 3H), 3.28-3.22 (m, 1H),
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1-Cyclohexyl-5,6-dimethoxy-2-(toluene-4-sulfonyl)-3-(4-
(m, 2H), 0.50-0.40 (m, 1H); 13C{1H} NMR (100 MHz, CDCl3):
δ 152.8, 149.8, 148.8, 142.0, 141.1, 139.1, 136.3, 132.4, 132.3,
129.3, 128.5 (2x), 128.2 (2x), 128.0 (2x), 127.4 (2x), 108.1,
105.4, 57.4, 56.3, 56.0, 39.8, 32.5, 27.2, 26.4, 26.14, 26.08.
trifluoromethylphenyl)-1H-indene (1l). 1l was synthesized ac-
cording to general synthetic procedure from 3u (115 mg, 0.2
mmol). Yield = 89% (99 mg); Colorless solid; mp = 223-225
oC (recrystallized from hexanes and EtOAc); HRMS (ESI-TOF)
m/z: [M + H]+ calcd for C31H32F3O4S 557.1973, found
1-Cyclohexyl-2-methanesulfonyl-5,6-dimethoxy-3-phenyl-
1H-indene (1p). 1p was synthesized according to general syn-
thetic procedure from 3y (86 mg, 0.2 mmol). Yield = 90% (74
1
557.1974; H NMR (400 MHz, CDCl3): δ 7.60 (br s, 4H), 7.32
o
(d, J = 8.0 Hz, 2H), 7.09 (s, 1H), 7.02 (d, J = 8.0 Hz, 2H), 6.40
(s, 1H), 4.07 (d, J = 2.8 Hz, 1H), 3.96 (s, 3H), 3.72 (s, 3H),
2.76-2.69 (m, 1H), 2.32 (s, 3H), 2.05-2.02 (m, 1H), 1.87-1.84
(m, 1H), 1.74-1.53 (m, 3H), 1.48-1.39 (m, 1H), 1.32-1.27 (m,
1H), 1.24-0.96 (m, 2H), 0.52-0.42 (m, 1H); 13C{1H} NMR (100
MHz, CDCl3): δ 150.4, 150.0, 149.0, 143.7, 142.7, 139.1,
138.7, 136.5, 135.7, 130.7, 130.5 (q, J = 32.6 Hz, 2x), 129.0
(2x), 127.5 (2x), 125.7 (q, J = 224.3 Hz), 124.9 (d, J = 3.8 Hz,
2x), 108.2, 105.0, 57.5, 56.3, 56.1, 39.8, 32.5, 27.2, 26.4, 26.2,
26.1, 21.4.
mg); Colorless solid; mp = 147-149 C (recrystallized from
9
hexanes and EtOAc); HRMS (ESI-TOF) m/z: [M + H]+ calcd
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for C24H29O4S 413.1787, found 413.1788; H NMR (400 MHz,
CDCl3): δ 7.54-7.48 (m, 5H), 7.11 (s, 1H), 6.66 (s, 1H), 4.05 (d,
J = 2.8 Hz, 1H), 3.97 (s, 3H), 3.78 (s, 3H), 2.66-2.59 (m, 1H),
2.64 (s, 3H), 2.04-2.01 (m, 1H), 1.85-1.77 (m, 1H), 1.73-1.69
(m, 3H), 1.66-1.59 (m, 2H), 1.25-0.97 (m, 2H), 0.58-0.47 (m,
1H); 13C{1H} NMR (100 MHz, CDCl3): δ 151.5, 149.9, 148.9,
140.8, 138.9, 135.8, 132.5, 129.2 (2x), 129.0, 128.7 (2x), 108.1,
105.5, 57.1, 56.3, 56.0, 44.3, 39.9, 32.4, 27.1, 26.5, 26.3, 26.2.
4-[3-Cyclohexyl-5,6-dimethoxy-2-(toluene-4-sulfonyl)-3H-
inden-1-yl]biphenyl (1m). 1m was synthesized according to
general synthetic procedure from 3v (116 mg, 0.2 mmol). Yield
1-Cyclohexyl-5,6-dimethoxy-2-(4-methoxybenzenesulfonyl)-
3-phenyl-1H-indene (1q). 1q was synthesized according to
general synthetic procedure from 3z (104 mg, 0.2 mmol). Yield
o
o
= 85% (96 mg); Colorless solid; mp = 254-256 C (recrystal-
= 91% (92 mg); Colorless solid; mp = 179-181 C (recrystal-
lized from hexanes and EtOAc); HRMS (ESI-TOF) m/z: [M +
lized from hexanes and EtOAc); HRMS (ESI-TOF) m/z: [M +
1
H]+ calcd for C36H37O4S 565.2413, found 565.2412; H NMR
1
H]+ calcd for C30H33O5S 505.2049, found 505.2051; H NMR
(400 MHz, CDCl3): δ 7.67-7.65 (m, 2H), 7.56 (br s, 4H), 7.52-
7.48 (m, 2H), 7.42-7.39 (m, 1H), 7.35 (d, J = 8.0 Hz, 2H), 7.10
(s, 1H), 6.99 (d, J = 8.0 Hz, 2H), 6.56 (s, 1H), 4.10 (d, J = 3.2
Hz, 1H), 3.96 (s, 3H), 3.74 (s, 3H), 2.78-2.71 (m, 1H), 2.30 (s,
3H), 2.06-2.04 (m, 1H), 1.88-1.84 (m, 1H), 1.75-1.65 (m, 3H),
1.48-1.39 (m, 1H), 1.32-1.27 (m, 1H), 1.24-0.85 (m, 2H), 0.53-
0.42 (m, 1H); 13C{1H} NMR (100 MHz, CDCl3): δ 152.0,
149.7, 148.8, 143.2, 141.7, 141.3, 140.5, 139.12, 139.10, 136.3,
131.5, 129.7 (2x), 128.9 (2x), 128.8 (2x), 127.6, 127.6 (2x),
127.0 (2x), 126.6 (2x), 108.1, 105.4, 57.5, 56.3, 56.1, 39.9,
32.5, 27.2, 26.5, 26.2, 26.1, 21.5.
(400 MHz, CDCl3): δ 7.38-7.32 (m, 5H), 7.34 (d, J = 8.8 Hz,
2H), 7.08 (s, 1H), 6.66 (d, J = 8.8 Hz, 2H), 6.48 (s, 1H), 4.06 (d,
J = 3.2 Hz, 1H), 3.94 (s, 3H), 3.76 (s, 3H), 3.70 (s, 3H), 2.76-
2.69 (m, 1H), 2.09-2.03 (m, 1H), 1.86-1.83 (m, 1H), 1.74-1.64
(m, 3H), 1.55-1.39 (m, 2H), 1.28-0.96 (m, 2H), 0.49-0.39 (m,
1H); 13C{1H} NMR (100 MHz, CDCl3): δ 162.6, 151.9, 149.6,
148.7, 141.8, 138.9, 136.4, 133.7, 132.5, 129.5 (2x), 129.0 (2x),
128.4, 127.9 (2x), 113.4 (2x), 108.1, 105.3, 57.3, 56.3, 55.9,
55.5, 39.8, 32.5, 27.2, 26.4, 26.10, 26.06. Single-crystal X-Ray
diagram: crystal of 1q was grown by slow diffusion of EtOAc
into a solution of 1q in CH2Cl2 to yield colorless prisms. The
compound crystallizes in the triclinic crystal system, space
group P - 1, a = 10.3709(18) Å , b = 111.1980(17) Å , c =
12.307(2) Å , V = 1245.4(4) Å 3, Z = 2, dcalcd = 1.346 g/cm3,
F(000) = 536, 2θ range 1.822~26.455o, R indices (all data) R1
= 0.0464, wR2 = 0.1100.
2-[3-Cyclohexyl-5,6-dimethoxy-2-(toluene-4-sulfonyl)-3H-
inden-1-yl]naphthalene (1n). 1n was synthesized according to
general synthetic procedure from 3w (111 mg, 0.2 mmol).
o
Yield = 86% (93 mg); Colorless solid; mp = 173-174 C (re-
crystallized from hexanes and EtOAc); HRMS (ESI-TOF) m/z:
[M + H]+ calcd for C34H35O4S 539.2256, found 539.2255; H
1
1-Cyclohexyl-2-(4-fluorobenzenesulfonyl)-5,6-dimethoxy-3-
phenyl-1H-indene (1r). 1r was synthesized according to gen-
eral synthetic procedure from 3aa (102 mg, 0.2 mmol). Yield =
92% (91 mg); Colorless solid; mp = 118-120 oC (recrystallized
from hexanes and EtOAc); HRMS (ESI-TOF) m/z: [M + H]+
calcd for C29H30FO4S 493.1849, found 493.1845; 1H NMR
(400 MHz, CDCl3): δ 7.42-7.32 (m, 7H), 7.09 (s, 1H), 6.87-
6.82 (m, 2H), 6.49 (s, 1H), 4.10 (d, J = 2.8 Hz, 1H), 3.95 (s,
3H), 3.71 (s, 3H), 2.75-2.68 (m, 1H), 2.05-2.03 (m, 1H), 1.87-
1.84 (m, 1H), 1.74-1.54 (m, 3H), 1.49-1.32 (m, 2H), 1.28-0.97
(m, 2H), 0.54-0.43 (m, 1H); 13C{1H} NMR (100 MHz, CDCl3):
δ 164.8 (d, J = 253.2 Hz), 152.7, 149.9, 148.9, 141.1, 139.0,
138.0 (d, J = 3.0 Hz), 136.1, 132.3, 130.2 (d, J = 9.8 Hz, 2x),
128.6 (2x), 128.1 (3x), 115.3 (d, J = 22.7 Hz, 2x), 108.1, 105.3,
57.5, 56.3, 56.0, 40.0, 32.4, 27.2, 26.4, 26.2, 26.1.
NMR (400 MHz, CDCl3): δ 7.90-7.79 (m, 4H), 7.58-7.54 (m,
3H), 7.25 (d, J = 8.8 Hz, 2H), 7.12 (s, 1H), 6.79 (d, J = 8.0 Hz,
2H), 6.49 (s, 1H), 4.14 (d, J = 2.8 Hz, 1H), 3.97 (s, 3H), 3.66 (s,
3H), 2.80-2.74 (m, 1H), 2.17 (br s, 3H), 2.09-2.05 (m, 1H),
1.89-1.85 (m, 1H), 1.77-1.63 (m, 3H), 1.49-1.36 (m, 1H), 1.32-
1.27 (m, 1H), 1.24-0.84 (m, 2H), 0.57-0.47 (m, 1H); 13C{1H}
NMR (100 MHz, CDCl3): δ 152.1, 149.7, 148.9, 143.2, 142.1,
139.0, 138.9, 136.6, 133.0, 132.8, 130.1, 128.7 (3x), 128.2 (2x),
127.7, 127.6 (3x), 126.6, 126.3, 108.1, 105.4, 57.5, 56.4, 56.0,
39.9, 32.5, 27.2, 26.5, 26.3, 26.2, 21.3.
2-Benzenesulfonyl-1-cyclohexyl-5,6-dimethoxy-3-phenyl-1H-
indene (1o). 1o was synthesized according to general synthetic
procedure from 3x (98 mg, 0.2 mmol). Yield = 88% (83 mg);
o
Colorless solid; mp = 172-173 C (recrystallized from hexanes
and EtOAc); HRMS (ESI-TOF) m/z: [M + H]+ calcd for
1-Cyclohexyl-2-(4-isopropylbenzenesulfonyl)-5,6-dimethoxy-
3-phenyl-1H-indene (1s). 1s was synthesized according to gen-
eral synthetic procedure from 3ab (107 mg, 0.2 mmol). Yield =
86% (89 mg); Colorless solid; mp = 133-135 oC (recrystallized
from hexanes and EtOAc); HRMS (ESI-TOF) m/z: [M + H]+
1
C29H31O4S 475.1943, found 475.1942; H NMR (400 MHz,
CDCl3): δ 7.43-7.35 (m, 6H), 7.33 (br s, 2H), 7.22-7.18 (m,
2H), 7.09 (s, 1H), 6.49 (s, 1H), 4.09 (d, J = 2.8 Hz, 1H), 3.95 (s,
3H), 3.71 (s, 3H), 2.76-2.69 (m, 1H), 2.06-2.04 (m, 1H), 1.86-
1.83 (m, 1H), 1.74-1.63 (m, 3H), 1.59-1.35 (m, 2H), 1.24-0.96
1
calcd for C32H37O4S 517.2413, found 517.2411; H NMR (400
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The Journal of Organic Chemistry
MHz, CDCl3): δ 7.35-7.26 (m, 7H), 7.09 (s, 1H), 7.03 (d, J =
CDCl3): δ 7.47 (d, J = 8.0 Hz, 2H), 7.44-7.41 (m, 3H), 7.30-
2
8.4 Hz, 2H), 6.48 (s, 1H), 4.09 (d, J = 3.2 Hz, 1H), 3.95 (s, 3H),
3.70 (s, 3H), 2.88-2.81 (m, 1H), 2.75-2.68 (m, 1H), 2.07-2.02
(m, 1H), 1.86-1.83 (m, 1H), 1.74-1.63 (m, 3H), 1.54-1.25 (m,
2H), 1.17 (d, J = 6.8 Hz, 3H), 1.16 (d, J = 7.2 Hz, 3H), 1.05-
0.97 (m, 2H), 0.51-0.41 (m, 1H); 13C{1H} NMR (100 MHz,
CDCl3): δ 153.8, 152.1, 149.6, 148.7, 141.5, 139.2, 139.0,
136.4, 132.5, 128.3, 129.8 (2x), 127.9 (2x), 127.6 (2x), 126.2
(2x), 108.1, 105.3, 57.4, 56.3, 56.0, 39.8, 34.0, 32.4, 27.2, 26.4,
26.2, 26.1, 23.6, 23.5.
7.27 (m, 2H), 7.13 (d, J = 8.0 Hz, 2H), 6.98 (s, 1H), 6.56 (d, J
= 0.4 Hz, 1H), 5.95 (s, 2H), 3.87 (s, 2H), 2.35 (s, 3H); 13C{1H}
NMR (100 MHz, CDCl3): δ 152.1, 148.8, 147.5, 143.6, 138.9,
138.2, 138.1, 137.5, 132.0, 129.3 (2x), 129.0 (2x), 128.7, 128.0
(2x), 127.4 (2x), 105.0, 103.3, 101.5, 39.7, 21.5.
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6
7
8
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4,5,6-Trimethoxy-3-phenyl-2-(toluene-4-sulfonyl)-1H-indene
(1x). 1x was synthesized according to general synthetic proce-
dure from 3aq (91 mg, 0.2 mmol). Yield = 83% (72 mg); Col-
orless solid; mp = 153-155 oC (recrystallized from hexanes and
EtOAc); HRMS (ESI-TOF) m/z: [M + H]+ Calcd for C25H25O5S
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20
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23
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27
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2-(4-n-Butylbenzenesulfonyl)-1-cyclohexyl-5,6-dimethoxy-3-
phenyl-1H-indene (1t). 1t was synthesized according to general
synthetic procedure from 3ac (110 mg, 0.2 mmol). Yield =
86% (91 mg); Colorless solid; mp = 138-140 oC (recrystallized
from hexanes and EtOAc); HRMS (ESI-TOF) m/z: [M + H]+
1
437.1423; Found 437.1432; H NMR (400 MHz, CDCl3): δ
7.39 (d, J = 8.0 Hz, 2H), 7.37-7.31 (m, 3H), 7.33-7.20 (m, 2H),
7.10 (d, J = 8.0 Hz, 2H), 6.88 (s, 1H), 3.92 (s, 2H), 3.89 (s, 3H),
3.75 (s, 3H), 3.26 (s, 3H), 2.34 (s, 3H); 13C{1H} NMR (100
MHz, CDCl3): δ 155.0, 151.7, 150.1, 143.4, 141.9, 139.3,
138.8, 137.9, 133.6, 129.6, 129.2 (2x), 128.5 (2x), 127.8, 127.4
(2x), 127.0 (2x), 103.7, 60.9, 60.8, 56.2, 40.1, 21.4.
1
calcd for C33H39O4S 531.2569, found 531.2567; H NMR (400
MHz, CDCl3): δ 7.39-7.31 (m, 7H), 7.09 (s, 1H), 6.99 (d, J =
8.4 Hz, 2H), 6.49 (s, 1H), 4.08 (d, J = 3.2 Hz, 1H), 3.95 (s, 3H),
3.71 (s, 3H), 2.75-2.69 (m, 1H), 2.55 (t, J = 7.6 Hz, 2H), 2.06-
2.03 (m, 1H), 1.86-1.83 (m, 1H), 1.74-1.63 (m, 3H), 1.55-1.37
(m, 4H), 1.33-1.05 (m, 4H), 0.90 (t, J = 7.2 Hz, 3H), 0.50-0.39
(m, 1H); 13C{1H} NMR (100 MHz, CDCl3): δ 152.3, 149.7,
148.8, 148.0, 141.5, 139.2, 139.0, 136.4, 132.5, 129.4 (2x),
128.4, 128.2 (2x), 127.9 (2x), 127.4 (2x), 108.1, 105.3, 57.4,
56.3, 56.0, 39.8, 35.4, 33.1, 32.5, 27.2, 26.4, 26.14, 26.09, 22.0,
13.8.
5,6-Dimethoxy-2-(toluene-4-sulfonyl)-3-(4-
trifluoromethylphenyl)-1H-indene (1y). 1y was synthesized
according to general synthetic procedure from 3ar (98 mg, 0.2
mmol). Yield = 82% (78 mg); Colorless solid; mp = 149-151
oC (recrystallized from hexanes and EtOAc); HRMS (ESI-TOF)
m/z: [M + H]+ Calcd for C25H22F3O4S 475.1191; Found
1
475.1196; H NMR (400 MHz, CDCl3): δ 7.70 (d, J = 8.0 Hz,
2H), 7.48 (d, J = 8.4 Hz, 2H), 7.43 (d, J = 8.0 Hz, 2H), 7.15 (d,
J = 8.0 Hz, 2H), 7.08 (s, 1H), 6.51 (s, 1H), 3.93 (s, 3H), 3.91 (s,
2H), 3.74 (s, 3H), 2.36 (s, 3H); 13C{1H} NMR (100 MHz,
CDCl3): δ 150.6, 150.5, 149.2, 144.0, 139.1, 138.6, 136.9,
136.1, 136.0, 129.5 (4x), 129.1, 127.4 (2x), 126.0 (q, J = 270.3
Hz), 125.0 (q, J = 3.8 Hz, 2x), 107.3, 105.1, 56.23, 56.17, 39.8,
21.4.
8-Cyclopentyl-4-methoxy-2-methyl-6-phenyl-7-(toluene-4-
sulfonyl)-1,8-dihydro-2H-3-oxaasindacene (1u). 1u was syn-
thesized according to general synthetic procedure from 3an
(106 mg, 0.2 mmol). Yield = 80% (80 mg); Colorless solid; mp
= 167-169 oC (recrystallized from hexanes and EtOAc); HRMS
(ESI-TOF) m/z: [M + H]+ calcd for C31H33O4S 501.2100, found
1
501.2101; H NMR (400 MHz, CDCl3): δ 7.36-7.33 (m, 2H),
5,6-Dimethoxy-3-(4-nitrophenyl)-2-(toluene-4-sulfonyl)-1H-
indene (1z). 1z was synthesized according to general synthetic
procedure from 3as (94 mg, 0.2 mmol). Yield = 75% (68 mg);
7.30 (br s, 3H), 7.22 (d, J = 8.4 Hz, 2H), 6.92 (d, J = 8.0 Hz,
2H), 6.38 (s, 1H), 5.13-5.08 (m, 1H), 4.38 (d, J = 3.2 Hz, 1H),
3.70 (s, 3H), 3.52 (dd, J = 9.2, 15.6 Hz, 1H), 3.08-3.02 (m, 1H),
2.93 (dd, J = 6.8, 15.6 Hz, 1H), 2.28 (s, 3H), 1.78-1.69 (m, 2H),
1.62-1.39 (m, 5H), 1.49 (d, J = 6.4 Hz, 3H), 1.23-1.15 (m, 1H);
13C{1H} NMR (100 MHz, CDCl3): δ 152.2, 149.4, 144.2, 142.9,
142.2, 139.3, 137.4, 136.2, 132.7, 128.6 (2x), 128.4, 127.9 (4x),
127.5 (2x), 123.7, 105.8, 80.8, 56.0, 53.6, 41.8, 37.7, 30.2, 28.0,
25.0, 24.9, 21.8, 21.4.
o
Colorless solid; mp = 190-192 C (recrystallized from hexanes
and EtOAc); HRMS (ESI-TOF) m/z: [M + H]+ Calcd for
1
C24H22NO6S 452.1168; Found 452.1162; H NMR (400 MHz,
CDCl3): δ 8.32 (d, J = 8.8 Hz, 2H), 7.55-7.51 (m, 4H), 7.21 (d,
J = 8.4 Hz, 2H), 7.08 (s, 1H), 6.48 (s, 1H), 3.92 (s, 3H), 3.88 (s,
2H), 3.73 (s, 3H), 2.37 (s, 3H); 13C{1H} NMR (100 MHz,
CDCl3): δ 150.8, 149.7, 149.2, 147.9, 144.2, 139.3, 139.2,
138.5, 136.0, 135.6, 130.1 (2x), 129.7 (2x), 127.3 (2x), 123.3
(2x), 107.4, 104.9, 56.2, 56.1, 39.8, 21.5. Single-crystal X-Ray
diagram: crystal of 1z was grown by slow diffusion of EtOAc
into a solution of 1z in CH2Cl2 to yield colorless prisms. The
compound crystallizes in the monoclinic crystal system, space
group P 21/n, a = 14.6355(18) Å , b = 8.3230(10) Å , c =
17.421(2) Å , V = 2098.0(4) Å 3, Z = 4, dcalcd = 1.429 g/cm3,
F(000) = 944, 2θ range 1.697~26.424o, R indices (all data) R1
= 0.0519, wR2 = 0.1143.
5,6-Dimethoxy-3-phenyl-2-(toluene-4-sulfonyl)-1H-indene
(1v). 1v was synthesized according to general synthetic proce-
dure from 3ao (85 mg, 0.2 mmol). Yield = 78% (63 mg); Col-
orless solid; mp = 153-155 oC (recrystallized from hexanes and
EtOAc); HRMS (ESI-TOF) m/z: [M + H]+ Calcd for C24H23O4S
1
407.1317; Found 407.1322; H NMR (400 MHz, CDCl3): δ
7.47-7.43 (m, 5H), 7.33-7.31 (m, 2H), 7.12 (d, J = 8.4 Hz, 2H),
7.07 (s, 1H), 6.60 (d, J = 0.4 Hz, 1H), 3.92 (s, 3H), 3.90 (s, 2H),
3.73 (s, 3H), 2.34 (s, 3H); 13C{1H} NMR (100 MHz, CDCl3): δ
152.3, 150.3, 149.0, 143.5, 138.9, 137.9, 136.7, 135.9, 132.1,
129.3 (2x), 129.0 (2x), 128.6, 128.0 (2x), 127.3 (2x), 107.2,
105.5, 56.2, 56.1, 39.8, 21.4.
General synthetic procedure of skeletons 2 and 7 is as fol-
lows: NaBH4 (38 mg, 1.0 mmol) was added to a solution of 4,
3v-3w and 3ad (0.3 mmol) in THF and MeOH (v/v =1/1, 10
o
o
7-Phenyl-6-(toluene-4-sulfonyl)-5H-indeno[5,6-
mL) at 25 C. The reaction mixture was stirred at 25 C for 30
min. The reaction mixture was cooled to 25 oC and the solvent
was concentrated. The residue was diluted with water (10 mL)
and the mixture was extracted with CH2Cl2 (3 x 20 mL). The
combined organic layers were washed with brine (2 x 10 mL),
dried (MgSO4), filtered and evaporated to afford crude product
d][1,3]dioxole (1w). 1w was synthesized according to general
synthetic procedure from 3ap (82 mg, 0.2 mmol). Yield = 74%
(58 mg); Colorless solid; mp = 170-172 oC (recrystallized from
hexanes and EtOAc); HRMS (ESI-TOF) m/z: [M + H]+ Calcd
for C23H19O4S 391.1004; Found 391.1007; 1H NMR (400 MHz,
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1
2
3
4
5
6
7
8
under reduced pressure. Without further purification, A-15
7.70 (d, J = 8.0 Hz, 2H), 7.20 (d, J = 8.0 Hz, 2H), 7.18-7.12 (m,
(100 mg) was added to a solution of the resulting crude prod-
3H), 7.11 (d, J = 8.4 Hz, 1H), 6.95-6.92 (m, 2H), 6.75 (dd, J =
2.0, 8.4 Hz, 1H), 6.36 (d, J = 1.6 Hz, 1H), 4.84 (d, J = 6.4 Hz,
1H), 4.06 (dt, J = 6.4, 9.2 Hz, 1H), 3.60 (s, 3H), 3.51 (dd, J =
6.8, 16.8 Hz, 1H), 3.30 (dd, J = 9.2, 16.8 Hz, 1H), 2.35 (s, 3H);
13C{1H} NMR (100 MHz, CDCl3): δ 159.3, 145.0, 144.5, 142.4,
135.1, 131.2, 129.6 (2x), 128.4 (4x), 127.9 (2x), 126.7, 124.8,
114.0, 109.9, 71.8, 55.1, 52.3, 32.1, 21.4.
o
ucts in a toluene (10 mL) at 25 C. The reaction mixture was
stirred at reflux for 10 h under Dean-Stark distillation appa-
ratus. A-15 was filtered by filter paper and the A-15 was
washed with toluene (3 x 5 mL). The combined organic layers
were concentrated. The residue was diluted with saturated
NaHCO3(aq) (10 mL) and the mixture was extracted with
CH2Cl2 (3 x 20 mL). The combined organic layers were
washed with brine (2 x 10 mL), dried (MgSO4), filtered and
evaporated to afford crude product mixture under reduced pres-
sure. The remaining mixture was separated by column chroma-
tography (silica gel, hexanes/EtOAc = 8/1~4/1 as eluent) af-
fording 2 and 7.
9
5,6,7-Trimethoxy-1-phenyl-2-(toluene-4-sulfonyl)indan (2e).
2e was synthesized according to general synthetic procedure
from 4e (136 mg, 0.3 mmol). Yield = 91% (120 mg); Colorless
solid; mp = 169-171 oC (recrystallized from hexanes and
EtOAc); HRMS (ESI-TOF) m/z: [M + H]+ Calcd for C25H27O5S
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
1
439.1579; Found 439.1581; H NMR (400 MHz, CDCl3): δ
5,6-Dimethoxy-1-phenyl-2-(toluene-4-sulfonyl)indan (2a).
2a was synthesized according to general synthetic procedure
from 4a (127 mg, 0.3 mmol). Yield = 84% (103 mg); Colorless
solid; mp = 152-154 oC (recrystallized from hexanes and
EtOAc); HRMS (ESI-TOF) m/z: [M + H]+ Calcd for C24H25O4S
7.68 (d, J = 8.4 Hz, 2H), 7.20 (d, J = 8.4 Hz, 2H), 7.13-7.05 (m,
3H), 6.83 (d, J = 8.4 Hz, 2H), 6.49 (s, 1H), 4.87 (d, J = 3.6 Hz,
1H), 3.82 (dt, J = 3.6, 8.8 Hz, 1H), 3.75 (s, 3H), 3.69 (s, 3H),
3.44 (dd, J = 4.4, 17.6 Hz, 1H), 3.36 (dd, J = 9.2, 17.6 Hz, 1H),
3.28 (s, 3H), 2.33 (s, 3H); 13C{1H} NMR (100 MHz, CDCl3): δ
155.0, 149.3, 144.3, 143.1, 141.9, 135.2, 134.4, 129.4 (2x),
128.4 (2x), 128.1 (2x), 127.9, 126.8 (2x), 126.4, 102.5, 71.6,
60.3, 59.5, 55.7, 50.0, 32.9, 21.2. Single-crystal X-Ray diagram:
crystal of 2e was grown by slow diffusion of EtOAc into a
solution of 2e in CH2Cl2 to yield colorless prisms. The com-
pound crystallizes in the monoclinic crystal system, space
group P21/n, a = 11.9401(5) Å , b = 11.1292(5) Å , c =
17.5921(7) Å , V = 2281.61(17) Å 3, Z = 4, dcalcd = 1.277 g/cm3,
F(000) = 928, 2θ range 1.886~26.389o, R indices (all data) R1
= 0.0642, wR2 = 0.1588.
1
409.1474; Found 409.1476; H NMR (400 MHz, CDCl3): δ
7.69 (d, J = 8.0 Hz, 2H), 7.22 (d, J = 8.0 Hz, 2H), 7.18-7.12 (m,
3H), 6.89-6.87 (m, 2H), 6.72 (s, 1H), 6.32 (s, 1H), 4.79 (d, J =
5.6 Hz, 1H), 3.96 (dt, J = 6.0, 9.2 Hz, 1H), 3.82 (s, 3H), 3.65 (s,
3H), 3.48 (dd, J = 10.0, 16.4 Hz, 1H), 3.30 (dd, J = 9.2, 16.4
Hz, 1H), 2.37 (s, 3H); 13C{1H} NMR (100 MHz, CDCl3): δ
149.0, 148.8, 144.4, 142.8, 135.0, 134.9, 131.1, 129.5 (2x),
128.4 (2x), 128.3 (2x), 127.7 (2x), 126.7, 107.5, 106.7, 71.8,
55.8, 55.7, 52.1, 32.7, 21.3.
5-Phenyl-6-(toluene-4-sulfonyl)-6,7-dihydro-5H-indeno[5,6-
d][1,3]dioxole (2b). 2b was synthesized according to general
synthetic procedure from 4b (121 mg, 0.3 mmol). Yield = 86%
(101 mg); Colorless liquid; HRMS (ESI-TOF) m/z: [M + H]+
Calcd for C23H21O4S 393.1161; Found 393.1160; 1H NMR
(400 MHz, CDCl3): δ 7.69 (d, J = 8.4 Hz, 2H), 7.20 (d, J = 8.0
Hz, 2H), 7.18-7.12 (m, 3H), 6.92-6.90 (m, 2H), 6.63 (s, 1H),
6.24 (s, 1H), 5.82 (d, J = 1.2 Hz, 1H), 5.80 (d, J = 1.2 Hz, 1H),
4.74 (d, J = 6.0 Hz, 1H), 4.03 (dt, J = 6.4, 8.8 Hz, 1H), 3.45 (dd,
J = 6.4, 16.8 Hz, 1H), 3.25 (dd, J = 9.2, 16.8 Hz, 1H), 2.35 (s,
3H); 13C{1H} NMR (100 MHz, CDCl3): δ 147.4, 147.2, 144.3,
142.5, 136.1, 134.9, 131.9, 129.4 (2x), 128.3 (4x), 127.6 (2x),
126.6, 105.0, 104.0, 100.9, 71.6, 51.7, 32.4, 21.2.
1-Phenyl-2-(toluene-4-sulfonyl)indan (2f). 2f was synthe-
sized according to general synthetic procedure from 4f (109 mg,
0.3 mmol). Yield = 84% (88 mg); Colorless liquid; HRMS
(ESI-TOF) m/z: [M + H]+ Calcd for C22H21O2S 349.1262;
1
Found 349.1265; H NMR (400 MHz, CDCl3): δ 7.73 (d, J =
8.0 Hz, 2H), 7.25-7.17 (m, 7H), 7.12 (t, J = 7.6 Hz, 1H), 6.97-
6.95 (m, 2H), 6.84 (d, J = 8.0 Hz, 1H), 4.90 (d, J = 6.8 Hz, 1H),
4.10 (dt, J = 6.8, 8.8 Hz, 1H), 3.62 (dd, J = 6.8, 16.8 Hz, 1H),
3.40 (dd, J = 9.2, 16.8 Hz, 1H), 2.37 (s, 3H); 13C{1H} NMR
(100 MHz, CDCl3): δ 144.3, 143.5, 142.3, 139.1, 134.9, 129.4
(2x), 128.24 (2x), 128.21 (2x), 127.7 (2x), 127.3, 127.1, 126.6,
124.8, 123.9, 71.2, 52.0, 32.7, 21.2.
5-Methoxy-1-phenyl-2-(toluene-4-sulfonyl)indan (2c). 2c
was synthesized according to general synthetic procedure from
4c (118 mg, 0.3 mmol). Yield = 88% (100 mg); Colorless solid;
1-Phenyl-2-(toluene-4-sulfonyl)-2,3-dihydro-1H-
cyclopenta[a]naphthalene (2g). 2g was synthesized according
to general synthetic procedure from 4g (124 mg, 0.3 mmol).
o
o
mp = 107-109 C (recrystallized from hexanes and EtOAc);
Yield = 86% (103 mg); Colorless solid; mp = 169-171 C (re-
HRMS (ESI-TOF) m/z: [M + H]+ Calcd for C23H23O3S
crystallized from hexanes and EtOAc); HRMS (ESI-TOF) m/z:
1
1
379.1368; Found 379.1365; H NMR (400 MHz, CDCl3): δ
[M + H]+ Calcd for C26H23O2S 399.1419; Found 399.1418; H
7.71 (d, J = 8.0 Hz, 2H), 7.22 (d, J = 8.0 Hz, 2H), 7.18-7.14 (m,
3H), 6.94-6.92 (m, 2H), 6.77 (d, J = 1.6 Hz, 1H), 6.73 (d, J =
8.8 Hz, 1H), 6.68 (dd, J = 2.4, 8.4 Hz, 1H), 4.81 (d, J = 6.4 Hz,
1H), 4.06 (dt, J = 6.8, 8.8 Hz, 1H), 3.74 (s, 3H), 3.56 (dd, J =
6.4, 16.8 Hz, 1H), 3.35 (dd, J = 8.8, 16.8 Hz, 1H), 2.37 (s, 3H);
13C{1H} NMR (100 MHz, CDCl3): δ 159.3, 144.3, 142.7, 140.6,
135.5, 134.9, 129.4 (2x), 128.3 (2x), 128.2 (2x), 127.6 (2x),
126.5, 125.5, 113.6, 108.8, 71.6, 55.1, 51.3, 32.8, 21.2.
NMR (400 MHz, CDCl3): δ 7.82 (d, J = 7.6 Hz, 1H), 7.78 (d, J
= 8.4 Hz, 2H), 7.76 (d, J = 8.8 Hz, 1H), 7.37 (d, J = 8.0 Hz,
1H), 7.36 (d, J = 8.0 Hz, 2H), 7.29 (dd, J = 1.2, 6.4 Hz, 1H),
7.25 (d, J = 8.0 Hz, 2H), 7.20-7.16 (m, 3H), 6.90 (d, J = 8.8 Hz,
1H), 6.89 (d, J = 6.0 Hz, 1H), 5.410 (d, J = 2.8 Hz, 1H), 3.98
(dt, J = 3.6, 8.4 Hz, 1H), 3.66 (dd, J = 3.6, 17.6 Hz, 1H), 3.58
(dd, J = 8.4, 17.6 Hz, 1H), 2.39 (s, 3H); 13C{1H} NMR (100
MHz, CDCl3): δ 144.7, 143.0, 138.1, 137.3, 134.7, 133.3,
129.71, 129.68 (2x), 129.0, 128.81 (2x), 128.75 (2x), 128.4,
127.4 (2x), 126.9, 126.3, 125.2, 124.4, 122.3, 72.1, 51.6, 33.7,
21.5. Single-crystal X-Ray diagram: crystal of 2g was grown
by slow diffusion of EtOAc into a solution of 2g in CH2Cl2 to
yield colorless prisms. The compound crystallizes in the triclin-
6-Methoxy-1-phenyl-2-(toluene-4-sulfonyl)indan (2d). 2d
was synthesized according to general synthetic procedure from
4d (118 mg, 0.3 mmol). Yield = 86% (98 mg); Colorless liquid;
HRMS (ESI-TOF) m/z: [M + H]+ Calcd for C23H23O3S
1
379.1368; Found 379.1367; H NMR (400 MHz, CDCl3): δ
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The Journal of Organic Chemistry
ic crystal system, space group P - 1, a = 7.1922(6) Å , b =
group P21/n, a = 10.4333(7) Å , b = 8.3721(5) Å , c =
2
8.1888(7) Å , c = 17.2964(15) Å , V = 1007.88(15) Å 3, Z = 2,
dcalcd = 1.313 g/cm3, F(000) = 420, 2θ range 1.189~26.415o, R
indices (all data) R1 = 0.0896, wR2 = 0.1604.
20.9050(12) Å , V = 1813.91(19) Å 3, Z = 4, dcalcd = 1.565 g/cm3,
F(000) = 872, 2θ range 2.093~26.382o, R indices (all data) R1
= 0.0277, wR2 = 0.0609.
3
4
5
6-Chloro-1-phenyl-2-(toluene-4-sulfonyl)indan (2h). 2h was
synthesized according to general synthetic procedure from 4h
(119 mg, 0.3 mmol). Yield = 83% (95 mg); Colorless liquid;
HRMS (ESI-TOF) m/z: [M + H]+ Calcd for C22H20ClO2S
3-(3-Nitrophenyl)-1-phenyl-2-(toluene-4-sulfonyl)propan-1-
ol (7l). 7l was synthesized according to general synthetic pro-
cedure from 4l (122 mg, 0.3 mmol). Yield = 96% (118 mg);
6
7
8
9
o
Colorless solid; mp = 58-60 C (recrystallized from hexanes
1
383.0873; Found 383.0874; H NMR (400 MHz, CDCl3): δ
and EtOAc); HRMS (ESI-TOF) m/z: [M + H]+ Calcd for
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
1
7.69 (d, J = 8.4 Hz, 2H), 7.23 (d, J = 8.0 Hz, 2H), 7.19-7.14 (m,
5H), 6.89-6.86 (m, 2H), 6.80 (s, 1H), 4.80 (d, J = 6.4 Hz, 1H),
4.04 (dt, J = 6.4, 9.2 Hz, 1H), 3.54 (dd, J = 6.4, 17.2 Hz, 1H),
3.34 (dd, J = 9.2, 17.2 Hz, 1H), 2.40 (s, 3H); 13C{1H} NMR
(100 MHz, CDCl3): δ 145.7, 144.8, 141.8, 137.9, 135.0, 133.3,
129.7 (2x), 128.7, 128.6 (2x), 128.0, 127.93, 127.89 (2x), 127.1,
125.3 (2x), 71.6, 52.3, 32.5, 21.5.
C22H22NO5S 412.1219; Found 412.1221; H NMR (400 MHz,
CDCl3 + DMSO-d6): δ 7.68 (dd, J = 2.0, 8.0 Hz, 1H), 7.53 (d, J
= 8.0 Hz, 2H), 7.13-6.99 (m, 9H), 6.86 (d, J = 8.4 Hz, 1H),
5.02 (dd, J = 3.6, 7.6 Hz, 1H), 4.91 (d, J = 3.6 Hz, 1H), 3.66 (dt,
J = 5.6, 7.6 Hz, 1H), 2.98 (dd, J = 5.6, 15.2 Hz, 1H), 2.60 (dd,
J = 6.0, 15.2 Hz, 1H), 2.23 (s, 3H); 13C{1H} NMR (100 MHz,
CDCl3+ DMSO-d6): δ 147.3, 144.4, 139.5, 139.3, 135.6, 134.3,
129.3 (2x), 128.6, 128.1 (2x), 127.93, 127.88 (2x), 127.0 (2x),
122.9, 120.7, 72.1, 71.4, 31.2, 21.0. Single-crystal X-Ray dia-
gram: crystal of 7l was grown by slow diffusion of EtOAc into
a solution of 7l in CH2Cl2 to yield colorless prisms. The com-
pound crystallizes in the monoclinic crystal system, space
group P 21/c, a = 10.8179(10) Å , b = 10.4282(10) Å , c =
16.7152(16) Å , V = 1885.4(3) Å 3, Z = 4, dcalcd = 1.450 g/cm3,
F(000) = 864, 2θ range 1.883~26.422o, R indices (all data) R1
= 0.0546, wR2 = 0.0943.
3-(3,4-Dichlorophenyl)-1-phenyl-2-(toluene-4-
sulfonyl)propan-1-ol (7i). 7i was synthesized according to gen-
eral synthetic procedure from 4i (129 mg, 0.3 mmol). Yield =
96% (125 mg); Colorless liquid; HRMS (ESI-TOF) m/z: [M +
1
H]+ Calcd for C22H21Cl2O3S 435.0589; Found 435.0591; H
NMR (400 MHz, CDCl3): δ 7.65 (d, J = 8.4 Hz, 2H), 7.29 (br s,
1H), 7.28-7.23 (m, 6H), 7.03 (d, J = 8.8 Hz, 1H), 6.36-6.34 (m,
2H), 5.13 (d, J = 8.0 Hz, 1H), 4.48 (br s, 1H), 3.64 (dt, J = 6.0,
8.4 Hz, 1H), 2.95 (dd, J = 6.0, 15.2 Hz, 1H), 2.45 (dd, J = 6.0,
15.2 Hz, 1H), 2.45 (s, 3H); 13C{1H} NMR (100 MHz, CDCl3):
δ 145.5, 139.0, 137.4, 135.2, 131.9, 130.4, 130.3, 129.9, 129.8
(2x), 128.8, 128.6 (2x), 128.5 (2x), 127.6, 127.4 (2x), 73.2,
72.0, 31.9, 21.6.
3-Phenyl-2-(toluene-4-sulfonyl)indan-5-ol (2m). 2m was
synthesized according to general synthetic procedure from 4m
(113 mg, 0.3 mmol). Yield = 86% (94 mg); Colorless solid; mp
= 170-172 oC (recrystallized from hexanes and EtOAc); HRMS
(ESI-TOF) m/z: [M + H]+ Calcd for C22H21O3S 365.1212;
6-Fluoro-1-phenyl-2-(toluene-4-sulfonyl)indan (2j). 2j was
synthesized according to general synthetic procedure from 4j
(114 mg, 0.3 mmol). Yield = 88% (97 mg); Colorless liquid;
HRMS (ESI-TOF) m/z: [M + H]+ Calcd for C22H20FO2S
1
Found 365.1213; H NMR (400 MHz, CDCl3): δ 7.69 (d, J =
8.4 Hz, 2H), 7.22 (d, J = 8.0 Hz, 2H), 7.18-7.14 (m, 3H), 7.05
(d, J = 8.0 Hz, 1H), 6.91-6.89 (m, 2H), 6.67 (dd, J = 2.4, 8.0
Hz, 1H), 6.26 (d, J = 2.0 Hz, 1H), 4.88 (br s, 1H), 4.76 (d, J =
6.4 Hz, 1H), 4.02 (dt, J = 6.4, 9.2 Hz, 1H), 3.47 (dd, J = 6.4,
16.4 Hz, 1H), 3.28 (dd, J = 9.2, 16.4 Hz, 1H), 2.39 (s, 3H);
13C{1H} NMR (100 MHz, CDCl3): δ 155.4, 145.4, 144.6, 142.3,
135.2, 131.3, 129.7 (2x), 128.6 (2x), 128.5 (2x), 128.0 (2x),
126.9, 125.0, 115.2, 111.9, 71.9, 52.3, 32.2, 21.6.
1
367.1168; Found 367.1169; H NMR (400 MHz, CDCl3): δ
7.71 (d, J = 8.0 Hz, 2H), 7.22 (d, J = 8.0 Hz, 2H), 7.20-7.15 (m,
4H), 6.93-6.86 (m, 3H), 6.52 (dd, J = 2.0, 8.4 Hz, 1H), 4.83 (d,
J = 6.4 Hz, 1H), 4.08 (dt, J = 6.4, 9.2 Hz, 1H), 3.54 (dd, J = 6.4,
16.8 Hz, 1H), 3.34 (dd, J = 9.2, 16.8 Hz, 1H), 2.38 (s, 3H);
13C{1H} NMR (100 MHz, CDCl3): δ 162.4 (d, J = 243.3 Hz),
145.8 (d, J = 8.3 Hz), 144.6, 141.7, 134.9, 134.8 (d, J = 3.0 Hz),
129.6 (2x), 128.5 (2x), 128.4 (2x), 127.8 (2x), 127.0, 125.2 (d,
J = 8.4 Hz), 114.7 (d, J = 22.7 Hz), 111.9 (d, J = 22.0 Hz), 71.7,
52.2 (d, J = 1.5 Hz), 32.1, 21.4.
1,6-Diphenyl-2-(toluene-4-sulfonyl)indan (2n). 2n was syn-
thesized according to general synthetic procedure from 4n (131
mg, 0.3 mmol). Yield = 84% (107 mg); Colorless liquid;
HRMS (ESI-TOF) m/z: [M + H]+ Calcd for C28H25O2S
1
425.1575; Found 425.1578; H NMR (400 MHz, CDCl3): δ
4-Bromo-1-phenyl-2-(toluene-4-sulfonyl)indan (2k). 2k was
synthesized according to general synthetic procedure from 4k
(132 mg, 0.3 mmol). Yield = 87% (111 mg); Colorless solid;
7.74 (d, J = 8.4 Hz, 2H), 7.46-7.44 (m, 3H), 7.38-7.17 (m, 9H),
7.04 (s, 1H), 6.98-6.95 (m, 2H), 4.91 (d, J = 6.4 Hz, 1H), 4.09
(dt, J = 6.8, 8.8 Hz, 1H), 3.63 (dd, J = 6.8, 16.8 Hz, 1H), 3.43
(dd, J = 6.8, 16.8 Hz, 1H), 2.40 (s, 3H); 113C{1H} NMR (100
MHz, CDCl3): δ 144.6, 144.4, 142.5, 140.9, 140.8, 138.6,
135.2, 129.7 (2x), 128.64 (2x), 128.62 (2x), 128.58 (2x), 128.1
(2x), 127.2, 127.0 (2x), 126.9, 126.8, 124.5, 123.9, 71.8, 52.4,
32.8, 21.5.
o
mp = 131-133 C (recrystallized from hexanes and EtOAc);
HRMS (ESI-TOF) m/z: [M + H]+ Calcd for C22H20BrO2S
1
427.0367; Found 427.0368; H NMR (400 MHz, CDCl3): δ
7.72 (d, J = 8.4 Hz, 2H), 7.35 (d, J = 8.0 Hz, 1H), 7.24 (d, J =
8.8 Hz, 2H), 7.21-7.17 (m, 3H), 7.00 (t, J = 7.6 Hz, 1H), 6.93-
6.91 (m, 2H), 6.78 (d, J = 7.6 Hz, 1H), 4.96 (d, J = 6.4 Hz, 1H),
4.03 (dt, J = 6.4, 9.2 Hz, 1H), 3.57 (dd, J = 6.4, 17.6 Hz, 1H),
3.39 (dd, J = 9.2, 17.6 Hz, 1H), 2.39 (s, 3H); 13C{1H} NMR
(100 MHz, CDCl3): δ 145.4, 144.8, 142.1, 140.0, 134.8, 130.6,
129.7 (2x), 129.2, 128.6 (2x), 128.5 (2x), 127.8 (2x), 127.1,
124.0, 119.4, 70.4, 53.2, 34.5, 21.5. Single-crystal X-Ray dia-
gram: crystal of 2k was grown by slow diffusion of EtOAc into
a solution of 2k in CH2Cl2 to yield colorless prisms. The com-
pound crystallizes in the monoclinic crystal system, space
6-Methyl-1-phenyl-2-(toluene-4-sulfonyl)indan (2o). 2o was
synthesized according to general synthetic procedure from 4o
(113 mg, 0.3 mmol). Yield = 82% (89 mg); Colorless liquid;
HRMS (ESI-TOF) m/z: [M + H]+ Calcd for C23H23O2S
1
363.1419; Found 363.1423; H NMR (400 MHz, CDCl3): δ
7.73 (d, J = 8.4 Hz, 2H), 7.23 (d, J = 8.0 Hz, 2H), 7.22-7.18 (m,
3H), 7.14 (d, J = 7.6 Hz, 1H), 7.03 (d, J = 7.6 Hz, 1H), 6.97-
6.95 (m, 2H), 6.66 (s, 1H), 4.85 (d, J = 6.4 Hz, 1H), 4.08 (dt, J
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= 6.8, 8.8 Hz, 1H), 3.58 (dd, J = 6.8, 16.8 Hz, 1H), 3.37 (dd, J
= 9.2, 16.8 Hz, 1H), 2.40 (s, 3H), 2.23 (s, 3H); 13C{1H} NMR
(100 MHz, CDCl3): δ 144.4, 143.7, 142.6, 136.9, 136.2, 135.1,
129.54, 129.49 (2x), 128.4 (2x), 128.3 (2x), 127.9 (2x), 126.6,
125.4, 123.7, 71.5, 52.1, 32.5, 21.3, 21.0.
Calcd for C24H24FO4S 427.1379; Found 427.1384; H NMR
(400 MHz, CDCl3): δ 7.69 (d, J = 8.0 Hz, 2H), 7.24 (d, J = 8.0
Hz, 2H), 6.89-6.82 (m, 4H), 6.71 (s, 1H), 6.28 (s, 1H), 4.78 (d,
J = 6.0 Hz, 1H), 3.91 (dt, J = 6.4, 8.8 Hz, 1H), 3.83 (s, 3H),
3.67 (s, 3H), 3.46 (dd, J = 6.4, 16.4 Hz, 1H), 3.26 (dd, J = 9.2,
16.4 Hz, 1H), 2.39 (s, 3H); 13C{1H} NMR (100 MHz, CDCl3):
δ 161.6 (d, J = 244.1 Hz), 149.2, 149.0, 144.6, 138.7 (d, J = 3.8
Hz), 135.1, 134.8, 131.0, 129.6 (2x), 129.4 (d, J = 8.4 Hz, 2x),
128.5 (2x), 115.2 (d, J = 21.2 Hz, 2x), 107.5, 106.8, 72.0, 55.9,
55.8, 51.5, 32.8, 21.4.
4-Allyl-5,6-dimethoxy-1-phenyl-2-(toluene-4-sulfonyl)indan
(2p). 2p was synthesized according to general synthetic proce-
dure from 4p (139 mg, 0.3 mmol). Yield = 80% (108 mg);
9
o
Colorless solid; mp = 112-114 C (recrystallized from hexanes
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and EtOAc); HRMS (ESI-TOF) m/z: [M + H]+ Calcd for
1
C27H29O4S 449.1787; Found 449.1785; H NMR (400 MHz,
5,6-Dimethoxy-1-(4-methoxyphenyl)-2-(toluene-4-
CDCl3): δ 7.69 (d, J = 8.4 Hz, 2H), 7.23 (d, J = 8.0 Hz, 2H),
7.20-7.16 (m, 3H), 6.91-6.89 (m, 2H), 6.26 (s, 1H), 5.96-5.86
(m, 1H), 5.05 (dq, J = 1.6, 10.4 Hz, 1H), 4.97 (dq, J = 1.6, 17.2
Hz, 1H), 7.80 (d, J = 5.6 Hz, 1H), 3.95 (dt, J = 6.0, 8.8 Hz, 1H),
3.76 (s, 3H), 3.66 (s, 3H), 3.40 (dd, J = 6.0, 16.8 Hz, 1H), 3.37
(d, J = 6.0 Hz, 2H), 3.24 (dd, J = 9.2, 16.8 Hz, 1H), 2.40 (s,
3H); 13C{1H} NMR (100 MHz, CDCl3): δ 152.8, 146.9, 144.4,
142.8, 138.5, 135.7, 135.1, 131.4, 129.6 (2x), 128.7 (2x), 128.5
(3x), 127.9 (2x), 126.9, 115.3, 106.6, 71.7, 60.9, 55.7, 52.6,
31.7, 31.1, 21.5.
sulfonyl)indan (2u). 2u was synthesized according to general
synthetic procedure from 4u (136 mg, 0.3 mmol). Yield = 82%
(108 mg); Colorless solid; mp = 100-102 C (recrystallized
o
from hexanes and EtOAc); HRMS (ESI-TOF) m/z: [M + H]+
Calcd for C25H27O5S 439.1579; Found 439.1581; 1H NMR
(400 MHz, CDCl3): δ 7.68 (d, J = 8.4 Hz, 2H), 7.21 (d, J = 8.4
Hz, 2H), 6.80 (d, J = 8.8 Hz, 2H), 6.70 (s, 1H), 6.68 (d, J = 8.8
Hz, 2H), 6.31 (s, 1H), 4.74 (d, J = 6.0 Hz, 1H), 3.91 (dt, J = 6.4,
8.8 Hz, 1H), 3.81 (s, 3H), 3.70 (s, 3H), 3.65 (s, 3H), 3.46 (dd, J
= 6.4, 16.8 Hz, 1H), 3.26 (dd, J = 8.8, 16.8 Hz, 1H), 2.36 (s,
3H); 13C{1H} NMR (100 MHz, CDCl3): δ 158.2, 148.9, 148.8,
144.3, 135.2, 135.1, 134.8, 130.9, 129.5 (2x), 128.7 (2x), 128.4
(2x), 113.7 (2x), 107.5, 106.6, 71.9, 55.74, 55.68, 54.9, 51.3,
32.6, 21.3.
1-Phenyl-3-pyridin-3-yl-2-(toluene-4-sulfonyl)propan-1-ol
(7q). 7q was synthesized according to general synthetic proce-
dure from 4q (109 mg, 0.3 mmol). Yield = 96% (106 mg);
Colorless liquid; HRMS (ESI-TOF) m/z: [M + H]+ Calcd for
1
C21H22NO3S 368.1320; Found 368.1322; H NMR (400 MHz,
5,6-Dimethoxy-2-(toluene-4-sulfonyl)-1-p-tolylindan (2v). 2v
was synthesized according to general synthetic procedure from
4v (131 mg, 0.3 mmol). Yield = 82% (104 mg); Colorless solid;
CDCl3): δ 8.16 (t, J = 3.2 Hz, 1H), 7.68-7.65 (m, 3H), 7.24 (d,
J = 8.0 Hz, 2H), 7.20-7.16 (m, 5H), 6.88 (br s, 1H), 6.87 (d, J =
1.6 Hz, 1H), 5.09 (d, J = 8.0 Hz, 1H), 4.20 (br s, 1H), 3.72-3.67
(m, 1H), 3.04 (dd, J = 5.2, 15.2 Hz, 1H), 2.54 (dd, J = 6.8, 15.6
Hz, 1H), 2.38 (s, 3H); 13C{1H} NMR (100 MHz, CDCl3): δ
149.2, 147.1, 145.0, 139.1, 135.8, 135.4, 133.2, 129.8 (2x),
128.51, 128.46 (2x), 128.4 (2x), 127.2 (2x), 122.9, 72.9, 71.7,
29.6, 21.5.
o
mp = 172-174 C (recrystallized from hexanes and EtOAc);
HRMS (ESI-TOF) m/z: [M + H]+ Calcd for C25H27O4S
1
423.1630; Found 423.1630; H NMR (400 MHz, CDCl3): δ
7.70 (d, J = 8.4 Hz, 2H), 7.23 (d, J = 8.0 Hz, 2H), 6.97 (d, J =
7.6 Hz, 2H), 6.78 (d, J = 8.0 Hz, 2H), 6.71 (s, 1H), 6.34 (s, 1H),
4.77 (d, J = 6.0 Hz, 1H), 3.93 (dt, J = 6.4, 8.8 Hz, 1H), 3.83 (s,
3H), 3.66 (s, 3H), 3.46 (dd, J = 6.4, 16.4 Hz, 1H), 3.28 (dd, J =
8.8, 16.4 Hz, 1H), 2.38 (s, 3H), 2.26 (s, 3H); 13C{1H} NMR
(100 MHz, CDCl3): δ 148.9, 148.8, 144.4, 139.8, 136.3, 135.1,
131.0, 129.5 (2x), 129.0 (2x), 128.4 (2x), 127.6 (3x), 107.5,
106.7, 71.9, 55.8, 55.7, 51.7, 32.7, 21.3, 20.9.
4-Phenyl-5-(toluene-4-sulfonyl)-5,6-dihydro-4H-
cyclopenta[b]thiophene (2r). 2r was synthesized according to
general synthetic procedure from 4r (110 mg, 0.3 mmol). Yield
o
= 80% (85 mg); Colorless solid; mp = 109-111 C (recrystal-
lized from hexanes and EtOAc); HRMS (ESI-TOF) m/z: [M +
H]+ Calcd for C20H19O2S2 355.0827; Found 355.0826; 1H NMR
(400 MHz, CDCl3): δ 7.75 (d, J = 8.0 Hz, 2H), 7.28 (d, J = 8.0
Hz, 2H), 7.22-7.17 (m, 3H), 7.15 (d, J = 5.2 Hz, 1H), 6.96-6.93
(m, 2H), 6.51 (d, J = 4.8 Hz, 1H), 4.78 (d, J = 4.8 Hz, 1H),
4.27 (dt, J = 5.2, 9.2 Hz, 1H), 3.51 (dd, J = 5.2, 16.4 Hz, 1H),
3.33 (dd, J = 9.2, 16.4 Hz, 1H), 2.41 (s, 3H); 13C{1H} NMR
(100 MHz, CDCl3): δ 146.1, 144.7, 142.3, 138.6, 134.8, 129.6
(2x), 129.4, 128.5 (2x), 128.4 (2x), 127.3 (2x), 126.9, 121.8,
76.2, 48.2, 29.6, 21.4. Single-crystal X-Ray diagram: crystal of
2r was grown by slow diffusion of EtOAc into a solution of 2r
in CH2Cl2 to yield colorless prisms. The compound crystallizes
in the monoclinic crystal system, space group C2/c, a =
17.258(3) Å , b = 11.1864(19) Å , c = 17.603(3) Å , V =
3377.5(10) Å 3, Z = 8, dcalcd = 1.394 g/cm3, F(000) = 1488, 2θ
range 2.174~26.580o, R indices (all data) R1 = 0.0713, wR2 =
0.1309.
3-(3,4-Dimethoxyphenyl)-2-(toluene-4-sulfonyl)-1-(4-
trifluoromethylphenyl)propan-1-ol (7w). 7w was synthesized
according to general synthetic procedure from 4w (147 mg, 0.3
mmol). Yield = 98% (145 mg); Colorless solid; mp = 121-123
oC (recrystallized from hexanes and EtOAc); HRMS (ESI-TOF)
m/z: [M + H]+ Calcd for C25H26F3O5S 495.1453; Found
1
495.1456; H NMR (400 MHz, CDCl3): δ 7.54 (d, J = 8.4 Hz,
2H), 7.33 (d, J = 8.4 Hz, 2H), 7.22 (d, J = 8.4 Hz, 2H), 7.15 (d,
J = 8.4 Hz, 2H), 6.53 (d, J = 8.0 Hz, 1H), 6.23 (br s, 1H), 6.22
(dd, J = 2.0, 8.0 Hz, 1H), 5.09 (t, J = 6.0 Hz, 1H), 4.54 (br d, J
= 5.6 Hz, 1H), 3.75 (s, 3H), 3.74-3.70 (m, 1H), 3.67 (s, 3H),
3.21 (dd, J = 4.4, 14.8 Hz, 1H), 2.69 (dd, J = 8.8, 14.8 Hz, 1H),
2.35 (s, 3H); 13C{1H} NMR (100 MHz, CDCl3): δ 148.7, 147.7,
144.9, 143.6, 135.4, 129.7, 129.6 (2x), 129.0, 128.2 (2x),
127.05 (2x), 126.2 (q, J = 269.9 Hz), 124.9 (q, J = 3.8 Hz, 2x),
120.6, 111.4, 111.1, 71.4, 71.2, 55.7, 55.5, 31.3, 21.3.
1-(4-Fluorophenyl)-5,6-dimethoxy-2-(toluene-4-
3-(3,4-Dimethoxyphenyl)-1-(4-nitrophenyl)-2-(toluene-4-
sulfonyl)propan-1-ol (7x). 2x was synthesized according to
general synthetic procedure from 4x (140 mg, 0.3 mmol). Yield
= 94% (133 mg); Colorless liquid; HRMS (ESI-TOF) m/z: [M
sulfonyl)indan (2t). 2t was synthesized according to general
synthetic procedure from 4t (132 mg, 0.3 mmol). Yield = 82%
o
(105 mg); Colorless solid; mp = 164-166 C (recrystallized
from hexanes and EtOAc); HRMS (ESI-TOF) m/z: [M + H]+
+ H]+ Calcd for C24H26NO7S 472.1430; Found 472.1430; H
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NMR (400 MHz, CDCl3): δ 7.91 (d, J = 8.8 Hz, 2H), 7.53 (d, J
Hz), 149.2, 149.1, 142.5, 134.9, 134.3, 131.3 (d, J = 9.9 Hz,
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8
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= 8.4 Hz, 2H), 7.29 (d, J = 8.8 Hz, 2H), 7.15 (d, J = 8.0 Hz,
2H), 6.52 (d, J = 8.8 Hz, 1H), 6.26-6.24 (m, 2H), 5.14 (t, J =
5.6 Hz, 1H), 4.50 (br d, J = 5.2 Hz, 1H), 3.76-3.74 (m, 1H),
3.74 (s, 3H), 3.65 (s, 3H), 3.13 (dd, J = 4.4, 14.8 Hz, 1H), 2.70
(dd, J = 8.8, 14.8 Hz, 1H), 2.33 (s, 3H); 13C{1H} NMR (100
MHz, CDCl3): δ 148.7, 147.7, 147.1, 147.0, 145.0, 135.2,
129.5 (2x), 128.5, 128.2 (2x), 127.5 (2x), 122.9 (2x), 120.6,
111.5, 111.1, 71.0 (2x), 55.7, 55.5, 31.4, 21.3.
2x), 130.9, 128.6 (2x), 127.8 (2x), 127.0, 116.3 (d, J = 22.0 Hz,
2x), 107.6, 106.8, 72.1, 55.94, 55.90, 52.4, 32.7.
5,6-Dimethoxy-2-(4-methoxybenzenesulfonyl)-1-phenylindan
(2ac). 2ac was synthesized according to general synthetic pro-
cedure from 4ac (131 mg, 0.3 mmol). Yield = 86% (109 mg);
Colorless liquid; HRMS (ESI-TOF) m/z: [M + H]+ Calcd for
1
C24H25O5S 425.1423; Found 425.1421; H NMR (400 MHz,
CDCl3): δ 7.75 (d, J = 8.4 Hz, 2H), 7.20-7.15 (m, 3H), 6.91-
6.87 (m, 4H), 6.72 (s, 1H), 6.32 (s, 1H), 4.78 (d, J = 5.6 Hz,
1H), 3.95 (dt, J = 5.6, 9.2 Hz, 1H), 3.84 (s, 3H), 3.83 (s, 3H),
3.67 (s, 3H), 3.48 (dd, J = 6.0, 16.4 Hz, 1H), 3.32 (dd, J = 8.8,
16.4 Hz, 1H); 13C{1H} NMR (100 MHz, CDCl3): δ 163.6,
149.1, 149.0, 142.9, 135.1, 131.3, 130.7 (2x), 129.6, 128.5 (2x),
127.8 (2x), 126.8, 114.2 (2x), 107.7, 106.8, 72.2, 55.90, 55.87,
55.6, 52.4, 32.8.
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4-[5,6-Dimethoxy-2-(toluene-4-sulfonyl)indan-1-yl]biphenyl
(2y). 2y was synthesized according to general synthetic proce-
dure from 4y (149 mg, 0.3 mmol). Yield = 86% (125 mg);
Colorless liquid; HRMS (ESI-TOF) m/z: [M + H]+ Calcd for
1
C30H29O4S 485.1787; Found 485.1788; H NMR (400 MHz,
CDCl3): δ 7.74 (d, J = 8.0 Hz, 2H), 7.55-7.53 (m, 2H), 7.44-
7.41 (m, 4H), 7.35-7.31 (m, 1H), 7.25 (d, J = 8.0 Hz, 2H), 6.98
(d, J = 8.0 Hz, 2H), 6.75 (s, 1H), 6.39 (s, 1H), 4.87 (d, J = 5.6
Hz, 1H), 4.02 (dt, J = 6.0, 9.2 Hz, 1H), 3.87 (s, 3H), 3.71 (s,
3H), 3.52 (dd, J = 6.4, 16.8 Hz, 1H), 3.34 (dd, J = 9.2, 16.8 Hz,
1H), 2.39 (s, 3H); 13C{1H} NMR (100 MHz, CDCl3): δ 149.2,
149.1, 144.6, 141.9, 140.5, 139.8, 135.3, 135.0, 131.2, 129.6
(2x), 128.7 (2x), 128.6 (2x), 128.3 (2x), 127.23, 127.18 (2x),
126.9 (2x), 107.7, 106.8, 72.0, 55.9 (2x), 52.0, 32.9, 21.5.
2-(4-Ethylbenzenesulfonyl)-5,6-dimethoxy-1-phenylindan
(2ad). 2ad was synthesized according to general synthetic pro-
cedure from 4ad (131 mg, 0.3 mmol). Yield = 84% (106 mg);
Colorless liquid; HRMS (ESI-TOF) m/z: [M + H]+ Calcd for
1
C25H27O4S 423.1630; Found 423.1631; H NMR (400 MHz,
CDCl3): δ 7.73 (d, J = 8.4 Hz, 2H), 7.25 (d, J = 8.4 Hz, 2H),
7.17-7.12 (m, 3H), 6.87-6.85 (m, 2H), 6.73 (s, 1H), 6.32 (s,
1H), 4.79 (d, J = 6.0 Hz, 1H), 3.97 (dt, J = 6.0, 8.8 Hz, 1H),
3.84 (s, 3H), 3.66 (s, 3H), 3.51 (dd, J = 6.0, 16.8 Hz, 1H), 3.32
(dd, J = 8.8, 16.8 Hz, 1H), 2.67 (q, J = 7.6 Hz, 2H), 1.22 (t, J =
7.6 Hz, 3H); 13C{1H} NMR (100 MHz, CDCl3): δ 150.6, 149.0,
148.9, 142.8, 135.2, 135.0, 131.2, 128.6 (2x), 128.4 (4x), 127.7
(2x), 126.7, 107.6, 106.7, 71.8, 55.82, 55.78, 52.3, 32.6, 28.7,
15.1.
2-[5,6-Dimethoxy-2-(toluene-4-sulfonyl)indan-1-
yl]naphthalene (2z). 2z was synthesized according to general
synthetic procedure from 4z (142 mg, 0.3 mmol). Yield = 87%
(120 mg); Colorless solid; mp = 99-102 oC (recrystallized from
hexanes and EtOAc); HRMS (ESI-TOF) m/z: [M + H]+ Calcd
for C28H27O4S 459.1630; Found 459.1629; 1H NMR (400 MHz,
CDCl3): δ 7.77-7.75 (m, 1H), 7.70-7.61 (m, 4H), 7.47-7.42 (m,
2H), 7.23 (s, 1H), 7.13 (d, J = 8.0 Hz, 2H), 7.01 (dd, J = 1.6,
8.4 Hz, 1H), 6.79 (s, 1H), 6.32 (s, 1H), 4.91 (d, J = 6.4 Hz, 1H),
4.10 (dt, J = 6.8, 9.2 Hz, 1H), 3.88 (s, 3H), 3.64 (s, 3H), 3.60
(dd, J = 6.8, 16.8 Hz, 1H), 3.40 (dd, J = 9.2, 16.8 Hz, 1H), 2.24
(s, 3H); 13C{1H} NMR (100 MHz, CDCl3): δ 149.2, 149.1,
144.6, 139.9, 135.3, 135.0, 133.1, 132.3, 131.2, 129.5 (2x),
128.5 (3x), 127.6, 127.5, 127.1, 126.1, 125.7, 125.4, 107.7,
106.9, 71.6, 56.0, 55.9, 52.7, 32.6, 21.3.
2-(4-t-Butylbenzenesulfonyl)-5,6-dimethoxy-1-phenylindan
(2ae). 2ae was synthesized according to general synthetic pro-
cedure from 4ae (139 mg, 0.3 mmol). Yield = 86% (116 mg);
Colorless liquid; HRMS (ESI-TOF) m/z: [M + H]+ Calcd for
1
C27H31O4S 451.1943; Found 451.1940; H NMR (400 MHz,
CDCl3): δ 7.74 (d, J = 8.4 Hz, 2H), 7.43 (d, J = 8.4 Hz, 2H),
7.15-7.11 (m, 3H), 6.85-6.82 (m, 2H), 6.73 (s, 1H), 6.30 (s,
1H), 4.77 (d, J = 6.0 Hz, 1H), 3.98 (dt, J = 6.0, 9.2 Hz, 1H),
3.85 (s, 3H), 3.67 (s, 3H), 3.54 (dd, J = 6.4, 16.8 Hz, 1H), 3.35
(dd, J = 9.2, 16.8 Hz, 1H), 1.31 (s, 9H); 13C{1H} NMR (100
MHz, CDCl3): δ 157.5, 149.1, 149.0, 142.8, 135.1, 135.0,
131.2, 128.44 (2x), 128.41 (2x), 127.8 (2x), 126.8, 126.0 (2x),
107.7, 106.8, 71.9, 55.90, 55.87, 52.5, 35.1, 32.6, 30.9 (3x).
2-Benzenesulfonyl-5,6-dimethoxy-1-phenylindan (2aa). 2aa
was synthesized according to general synthetic procedure from
4aa (122 mg, 0.3 mmol). Yield = 87% (103 mg); Colorless
liquid; HRMS (ESI-TOF) m/z: [M + H]+ Calcd for C23H23O4S
1
395.1317; Found 395.1318; H NMR (400 MHz, CDCl3): δ
7.85-7.82 (m, 2H), 7.58-7.54 (m, 1H), 7.46-7.42 (m, 2H), 7.19-
7.13 (m, 3H), 6.88-6.86 (m, 2H), 6.73 (s, 1H), 6.33 (s, 1H),
4.81 (d, J = 5.2 Hz, 1H), 3.98 (dt, J = 6.0, 9.2 Hz, 1H), 3.84 (s,
3H), 3.67 (s, 3H), 3.51 (dd, J = 6.0, 16.8 Hz, 1H), 3.33 (dd, J =
9.2, 16.8 Hz, 1H); 13C{1H} NMR (100 MHz, CDCl3): δ 149.1,
149.0, 142.8, 138.1, 134.9, 133.5, 131.1, 129.0 (2x), 128.5 (4x),
127.7 (2x), 126.9, 107.6, 106.7, 71.8, 55.9, 55.8, 52.2, 32.7.
2-Methanesulfonyl-5,6-dimethoxy-1-phenylindan (2af). 2af
was synthesized according to general synthetic procedure from
4af (104 mg, 0.3 mmol). Yield = 89% (89 mg); Colorless solid;
o
mp = 135-137 C (recrystallized from hexanes and EtOAc);
HRMS (ESI-TOF) m/z: [M + H]+ Calcd for C18H21O4S
1
333.1161; Found 333.1162; H NMR (400 MHz, CDCl3): δ
7.28-7.13 (m, 5H), 6.76 (s, 1H), 6.33 (s, 1H), 4.78 (d, J = 6.0
Hz, 1H), 3.83-3.78 (m, 1H), 3.79 (s, 3H), 3.61 (s, 3H), 3.40 (d,
J = 8.0 Hz, 2H), 2.57 (s, 3H); 13C{1H} NMR (100 MHz,
CDCl3): δ 149.0, 148.9, 142.3, 134.7, 130.5, 128.7 (2x), 127.8
(2x), 127.1, 107.4, 106.8, 70.9, 55.7, 55.6, 52.1, 38.9, 32.1.
2-(4-Fluorobenzenesulfonyl)-5,6-dimethoxy-1-phenylindan
(2ab). 2ab was synthesized according to general synthetic pro-
cedure from 4ab (128 mg, 0.3 mmol). Yield = 88% (109 mg);
Colorless liquid; HRMS (ESI-TOF) m/z: [M + H]+ Calcd for
1
C23H22FO4S 413.1223; Found 413.1225; H NMR (400 MHz,
2-(Butane-1-sulfonyl)-5,6-dimethoxy-1-phenylindan (2ag).
2ag was synthesized according to general synthetic procedure
from 4ag (116 mg, 0.3 mmol). Yield = 86% (96 mg); Colorless
liquid; HRMS (ESI-TOF) m/z: [M + H]+ Calcd for C21H27O4S
CDCl3): δ 7.85-7.80 (m, 2H), 7.21-7.16 (m, 3H), 7.13-7.07 (m,
2H), 6.90-6.87 (m, 2H), 6.73 (s, 1H), 6.31 (s, 1H), 4.77 (d, J =
6.0 Hz, 1H), 3.99 (dt, J = 6.0, 9.2 Hz, 1H), 3.85 (s, 3H), 3.67 (s,
3H), 3.51 (dd, J = 6.0, 16.4 Hz, 1H), 3.35 (dd, J = 9.2, 16.4 Hz,
1H); 13C{1H} NMR (100 MHz, CDCl3): δ 165.7 (d, J = 254.7
1
375.1630; Found 375.1629; H NMR (400 MHz, CDCl3): δ
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7
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7.34-7.19 (m, 5H), 6.78 (s, 1H), 6.31 (s, 1H), 4.79 (d, J = 7.2
(2x), 126.9 (2x), 107.8, 107.6, 75.1, 56.1, 55.9, 51.9, 50.9, 43.2,
30.7, 30.4, 26.5, 26.4, 26.1, 21.7.
Hz, 1H), 3.88 (dt, J = 7.2, 9.2 Hz, 1H), 3.85 (s, 3H), 3.66 (s,
3H), 3.50 (dd, J = 7.6, 16.4 Hz, 1H), 3.39 (dd, J = 9.2, 16.4 Hz,
1H), 2.75-2.62 (m, 2H), 1.71-1.61 (m, 1H), 1.50-1.39 (m, 1H),
1.28-1.12 (m, 2H), 0.75 (t, J = 7.2 Hz, 3H); 13C{1H} NMR
(100 MHz, CDCl3): δ 149.1, 149.0, 142.5, 135.2, 130.6, 128.9
(2x), 128.1 (2x), 127.4, 107.6, 106.8, 69.2, 55.9, 55.8, 52.4,
51.6, 31.8, 23.3, 21.4, 13.2.
1-(4-Fluorophenyl)-5,6-dimethoxy-3-phenyl-2-(toluene-4-
sulfonyl)indan (2ak). 2ak was synthesized according to general
synthetic procedure from 3ad (137 mg, 0.3 mmol). Yield =
62% (93 mg); Colorless solid; mp = 200-202 oC (recrystallized
from hexanes and EtOAc); HRMS (ESI, M++1) calcd for
1
C30H28FO4S 503.1692, found 503.1698; H NMR (400 MHz,
9
1-(3,4-Dichlorophenyl)-2-(toluene-4-sulfonyl)indan (2ah).
2ah was synthesized according to general synthetic procedure
from 4ah (129 mg, 0.3 mmol). Yield = 82% (102 mg); Color-
CDCl3): δ 7.64 (d, J = 8.0 Hz, 2H), 7.22-7.16 (m, 5H), 7.01-
6.87 (m, 6H), 6.39 (s, 1H), 6.38 (s, 1H), 4.92 (d, J = 6.0 Hz,
1H), 4.88 (d, J = 6.0 Hz, 1H), 3.90 (t, J = 6.0 Hz, 1H), 3.74 (s,
3H), 3.73 (s, 3H), 2.41 (s, 3H); 13C NMR (100 MHz, CDCl3): δ
161.7 (d, J = 244.1 Hz), 149.8, 144.8, 143.2 (2x), 139.2, 135.5,
135.0, 134.8, 129.8 (d, J = 7.6 Hz, 2x), 129.7 (2x), 128.7 (2x),
128.6 (2x), 128.2 (2x), 126.9, 115.4 (d, J = 21.2 Hz, 2x), 107.4,
107.2, 80.3, 56.0 (2x), 51.8, 51.0, 21.6.
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o
less solid; mp = 115-117 C (recrystallized from hexanes and
EtOAc); HRMS (ESI-TOF) m/z: [M + H]+ Calcd for
1
C22H19Cl2O2S 417.0483; Found 417.0485; H NMR (400 MHz,
CDCl3): δ 7.69 (d, J = 8.0 Hz, 2H), 7.27-7.21 (m, 5H), 7.15 (dt,
J = 2.4, 8.0 Hz, 1H), 6.87 (d, J = 2.4 Hz, 1H), 6.80 (dd, J = 2.4,
8.4 Hz, 1H), 6.77 (d, J = 7.6 Hz, 1H), 4.74 (d, J = 7.2 Hz, 1H),
3.98 (dt, J = 7.6, 9.2 Hz, 1H), 3.61 (dd, J = 7.6, 16.8 Hz, 1H),
3.37 (dd, J = 9.2, 16.8 Hz, 1H), 2.42 (s, 3H); 13C{1H} NMR
(100 MHz, CDCl3): δ 145.1, 142.7, 142.6, 139.3, 135.1, 132.4,
131.0, 130.5, 130.2, 129.8 (2x), 128.5 (2x), 128.0, 127.7, 127.5,
124.9, 124.4, 71.4, 51.6, 32.7, 21.6.
3-(3,4-Dichlorophenyl)indan-1-one (8). Freshly prepared
Na(Hg) (~6%, 1 g) was added to a solution of 2ah (83 mg, 0.2
o
mmol) in MeOH (10 mL) at 25 C. The reaction mixture was
stirred at 25 oC for 2 h. Mercury was filtered by filter paper and
the fitrates were concentrated. The residue was diluted with
saturated NaHCO3(aq) (10 mL) and the mixture was extracted
with CH2Cl2 (3 x 20 mL). The combined organic layers were
washed with brine (2 x 10 mL), dried (MgSO4), filtered and
evaporated to afford crude products under reduced pressure.
Without further purification, PDC (380 mg, 1.0 mmol) was
added to a solution of the resulting crude products in DMF (5
mL) at 25 oC. The reaction mixture was stirred at reflux for 2 h.
The reaction mixture was filtered, washed with CH2Cl2 (3 x 20
mL), and the fitrates were concentrated. The remaining mixture
was separated by column chromatography (silica gel, hex-
anes/EtOAc = 8/1~4/1 as eluent) affording 8. Yield = 64% of
two-step (35 mg); Colorless solid; mp = 113-115 oC
(recrystallized from hexanes and EtOAc); HRMS (ESI-TOF)
m/z: [M + H]+ Calcd for C15H11Cl2O 277.0187; Found
277.0188; 1H NMR (400 MHz, CDCl3): δ 7.82 (dd, J = 0.8, 7.6
Hz, 1H), 7.60 (dt, J = 1.6, 7.6 Hz, 1H), 7.45 (dt, J = 0.4, 7.6 Hz,
1H), 7.38 (d, J = 8.4 Hz, 1H), 7.27-7.25 (m, 1H), 7.00 (d, J =
2.0 Hz, 1H), 6.95 (dd, J = 2.0, 8.4 Hz, 1H), 4.54 (dd, J = 3.6,
8.0 Hz, 1H), 3.23 (dd, J = 8.0, 19.2 Hz, 1H), 2.62 (dd, J = 4.0,
19.2 Hz, 1H); 13C{1H} NMR (100 MHz, CDCl3): δ 204.9,
156.5, 143.9, 136.7, 135.3, 132.9, 131.1, 130.9, 129.6, 128.3,
126.9, 126.7, 123.7, 46.4, 43.5.
2-[3-Cyclohexyl-5,6-dimethoxy-2-(toluene-4-sulfonyl)indan-
1-yl]naphthalene (2ai). 2ai was synthesized according to gen-
eral synthetic procedure from 3w (167 mg, 0.3 mmol). Yield =
o
75% (122 mg); Colorless solid; mp = 230-232 C (recrystal-
lized from hexanes and EtOAc); HRMS (ESI, M++1) calcd for
1
C34H37O4S 541.2413, found 541.2410; H NMR (400 MHz,
CDCl3): δ 7.82 (d, J = 8.4 Hz, 2H), 7.78 (dd, J = 3.2, 9.2 Hz,
1H), 7.69 (d, J = 8.4 Hz, 1H), 7.57-7.55 (m, 1H), 7.46-7.41 (m,
2H), 7.33 (d, J = 8.0 Hz, 2H), 7.06-7.02 (m, 2H), 6.79 (s, 1H),
6.47 (s, 1H), 4.99 (d, J = 4.0 Hz, 1H), 3.92 (s, 3H), 3.75-3.71
(m, 1H), 3.71 (s, 3H), 2.62 (t, J = 4.0 Hz, 1H), 2.46 (s, 3H),
1.67-1.43 (m, 6H), 1.19-1.82 (m, 5H); 13C NMR (100 MHz,
CDCl3): δ 149.2, 149.1, 144.8, 140.7, 135.2, 135.1, 133.9,
133.0, 132.2, 129.8 (2x), 129.2 (2x), 128.2, 127.7, 127.5, 126.9,
126.1 (2x), 125.8, 107.8, 107.6, 74.7, 56.0, 55.9, 51.6 (2x),
43.2, 30.7, 30.4, 26.5, 26.4, 26.1, 21.6. Single-crystal X-Ray
diagram: crystal of 2ai was grown by slow diffusion of EtOAc
into a solution of 2ai in CH2Cl2 to yield colorless prisms. The
compound crystallizes in the monoclinic crystal system, space
group P 21/n, a = 10.2968(4) Å , b = 20.9708(10) Å , c =
14.9988(7) Å , V = 3199.4(2) Å 3, Z = 4, dcalcd = 1.243 g/cm3,
F(000) = 1280, 2θ range 1.683~26.400o, R indices (all data) R1
= 0.0603, wR2 = 0. 1142.
2-Phenyl-3-(toluene-4-sulfonyl)quinoline (9). SnCl2 was
added to a solution of 4ai (81 mg, 0.2 mmol) in CH2Cl2 (10 mL)
at 25 oC. The reaction mixture was stirred at 25 oC for 10 min.
HCl(aq) (12N, 1mL) was added to the reaction mixture at 25 oC.
4-[3-Cyclohexyl-5,6-dimethoxy-2-(toluene-4-sulfonyl)indan-
1-yl]biphenyl (2aj). 2aj was synthesized according to general
synthetic procedure from 3v (175 mg, 0.3 mmol). Yield = 70%
o
The reaction mixture was stirred at 25 C for 3 h. The residue
o
(119 mg); Colorless solid; mp = 238-240 C (recrystallized
was diluted with saturated NaHCO3(aq) (10 mL) and the mixture
was extracted with CH2Cl2 (3 x 20 mL). The combined organic
layers were washed with brine (2 x 10 mL), dried (MgSO4),
filtered and evaporated to afford crude product under reduced
pressure. The remaining mixture was separated by column
chromatography (silica gel, hexanes/EtOAc = 8/1~4/1 as eluent)
affording 9. Yield = 75% (54 mg); Colorless solid; mp = 179-
180 oC (recrystallized from hexanes and EtOAc); HRMS (ESI-
TOF) m/z: [M + H]+ Calcd for C22H18NO2S 360.1058; Found
360.1058; 1H NMR (400 MHz, CDCl3): δ 9.29 (s, 1H), 8.16 (d,
J = 8.4 Hz, 1H), 8.08 (d, J = 0.8, 8.0 Hz, 1H), 7.89 (dt, J = 1.2,
8.4 Hz, 1H), 7.71 (dt, J = 1.2, 8.4 Hz, 1H), 7.42-7.37 (m, 1H),
from hexanes and EtOAc); HRMS (ESI, M++1) calcd for
1
C36H39O4S 567.2569, found 567.2575; H NMR (400 MHz,
CDCl3): δ 7.84 (d, J = 8.4 Hz, 2H), 7.57-7.55 (m, 2H), 7.44-
7.41 (m, 4H), 7.37-7.31 (m, 3H), 6.93 (d, J = 8.0 Hz, 2H), 6.74
(s, 1H), 6.51 (s, 1H), 4.94 (d, J = 4.0 Hz, 1H), 3.90 (s, 3H),
3.76 (s, 3H), 3.65 (t, J = 4.0 Hz, 1H), 3.57 (t, J = 3.6 Hz, 1H),
2.47 (s, 3H), 2.05-1.60 (m, 4H), 1.57-1.38 (m, 3H), 1.24-1.01
(m, 2H), 0.99-0.78 (m, 2H); 13C NMR (100 MHz, CDCl3): δ
149.2, 149.0, 144.8, 142.6, 140.6, 139.6, 135.11, 135.05, 133.9,
129.8 (2x), 129.3 (2x), 128.8 (2x), 128.6 (2x), 127.3, 127.0
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o
7.30-7.26 (m, 2H), 7.21-7.19 (m, 2H), 7.12 (d, J = 8.0 Hz, 2H),
(35 mg); Colorless solid; mp = 76-78 C (recrystallized from
2
6.99 (d, J = 8.0 Hz, 2H), 2.33 (s, 3H); 13C{1H} NMR (100
MHz, CDCl3): δ 157.1, 148.7, 143.9, 138.9, 138.2, 136.9,
134.9, 132.8, 129.7 (2x), 129.4, 129.1 (2x), 129.0, 128.6, 128.1,
128.0 (2x), 127.5 (2x), 125.8, 21.5. Single-crystal X-Ray dia-
gram: crystal of 9 was grown by slow diffusion of EtOAc into
a solution of 9 in CH2Cl2 to yield colorless prisms. The com-
pound crystallizes in the monoclinic crystal system, space
group P 21/c, a = 12.5407(14) Å , b = 5.3966(6) Å , c = 25.050(3)
Å , V = 1692.5(3) Å 3, Z = 4, dcalcd = 1.411 g/cm3, F(000) = 752,
2θ range 1.626~26.451o, R indices (all data) R1 = 0.0542, wR2
= 0.0970.
hexanes and EtOAc); HRMS (ESI-TOF) m/z: [M + H]+ calcd
3
4
5
6
7
8
9
1
for C15H13O2 225.0916, found 225.0924; H NMR (400 MHz,
CDCl3): δ 7.95 (dd, J = 2.0, 8.0 Hz, 1H), 7.54-7.38 (m, 6H),
7.08-7.04 (m, 2H), 5.49 (dd, J = 2.8, 13.2 Hz, 1H), 3.10 (dd, J
= 13.2, 16.8 Hz, 1H), 2.90 (dd, J = 2.8, 16.8 Hz, 1H); 13C NMR
(100 MHz, CDCl3): δ 191.9, 161.5, 138.7, 136.2, 128.8 (2x),
128.7, 127.0, 126.1 (2x), 121.6, 120.9, 118.1, 79.6, 44.6.
6,7-Dimethoxy-1-phenylisoquinoline (12). A solution of 1%
OsO4 (3 mL, in THF) was added to a solution of 1v (120 mg,
0.3 mmol) in the co-solvent of THF (10 mL) and water (3 mL).
NMO (50% in water, 210 mg, 0.9 mmol) was added to the
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o
2-Phenyl-3-(toluene-4-sulfonyl)chroman (10). NaBH4 (38
mg, 1.0 mmol) was added to a solution of 4k (130 mg, 0.3
reaction mixture at 25 C. The reaction mixture was stirred at
o
o
60 C for 20 h. The reaction mixture was cooled to 25 C, and
NaIO4 (214 mg, 1.0 mmol) in water (1 mL) was added to the
reaction mixture. The reaction mixture was stirred at 60 C for
o
mmol) in THF and MeOH (v/v =1/1, 10 mL) at 25 C. The
o
o
reaction mixture was stirred at 25 C for 30 min. The reaction
mixture was cooled to 25 oC and the solvent was concentrated.
The residue was diluted with water (10 mL) and the mixture
was extracted with CH2Cl2 (3 x 20 mL). The combined organic
layers were washed with brine (2 x 10 mL), dried (MgSO4),
filtered and evaporated to afford crude product under reduced
pressure. Without further purification, K3PO4 (170 mg, 0.8
mmol), CuI (19 mg, 0.1 mmol), KI (50 mg, 0.3 mmol), 1,10-
phenanthroline (1,10-Phen, 36 mg, 0.2 mmol) were added to
the resulting crude products in a toluene (10 mL) at 25 oC. The
reaction mixture was stirred at reflux for 48 h. The reaction
mixture was cooled to 25 oC and the solvent was concentrated.
The residue was diluted with water (10 mL) and the mixture
was extracted with CH2Cl2 (3 x 20 mL). The combined organic
layers were washed with brine (2 x 10 mL), dried (MgSO4),
filtered and evaporated to afford crude product under reduced
pressure. The remaining mixture was separated by column
chromatography (silica gel, hexanes/EtOAc = 15/1~4/1 as elu-
ent) affording 10. Yield = 48% (52 mg); Colorless solid; mp =
10 h. The reaction mixture was cooled to 25 oC and the solvent
was concentrated. The residue was diluted with water (10 mL)
and the mixture was extracted with CH2Cl2 (3 x 20 mL). The
combined organic layers were washed with brine (2 x 10 mL),
dried (MgSO4), filtered and evaporated to afford crude product
under reduced pressure. Without further purification, NH4OAc
(77 mg, 1.0 mmol) was added to the resulting crude products in
MeOH (10 mL) at 25 oC. The reaction mixture was stirred at 60
oC for 10 h. The overall synthetic procedure had to be moni-
tored by TLC until the reaction was completed. The reaction
mixture was cooled to 25 oC and the solvent was concentrated.
The residue was diluted with water (10 mL) and the mixture
was extracted with CH2Cl2 (3 x 20 mL). The combined organic
layers were washed with brine (2 x 10 mL), dried (MgSO4),
filtered and evaporated to afford crude product under reduced
pressure. The remaining mixture was separated by column
chromatography (silica gel, hexanes/EtOAc = 10/1~4/1 as elu-
ent) affording 12. Yield = 27% (21 mg); Colorless liquid;
HRMS (ESI-TOF) m/z: [M + H]+ calcd for C17H16NO2
o
92-94 C (recrystallized from hexanes and EtOAc); HRMS
(ESI-TOF) m/z: [M + H]+ Calcd for C22H21O3S 365.1211;
266.1181, found 266.1188; H NMR (400 MHz, CDCl3): δ
1
1
Found 365.1219; H NMR (400 MHz, CDCl3): δ 7.50 (d, J =
8.47 (d, J = 5.6 Hz, 1H), 7.72-7.69 (m, 2H), 7.55-7.46 (m, 4H),
7.37 (s, 1H), 7.13 (s, 1H), 4.05 (s, 3H), 3.86 (s, 3H); 13C NMR
(100 MHz, CDCl3): δ 158.3, 152.7, 150.0, 141.3, 140.0, 133.8,
129.6 (2x), 128.4 (3x), 122.5, 118.7, 105.6, 105.0, 56.0, 55.9.
8.0 Hz, 2H), 7.18 (br s, 5H), 7.13 (d, J = 8.0 Hz, 2H), 7.01 (dt,
J = 1.6, 8.0 Hz, 1H), 6.69 (dd = 0.8, 8.0 Hz, 1H), 6.64 (dt, J =
1.2, 7.6 Hz, 1H), 6.55 (dd, J = 1.6, 7.6 Hz, 1H), 5.05 (d, J = 6.4
Hz, 1H), 4.00 (dt, J = 6.0, 7.6 Hz, 1H), 3.27 (dd, J = 5.2, 14.8
Hz, 1H), 2.85 (dd, J = 8.0, 14.8 Hz, 1H), 2.37 (s, 3H); 13C
NMR (100 MHz, CDCl3): δ 154.4, 144.5, 139.1, 136.1, 130.9,
129.5 (2x), 128.41, 128.36 (2x), 128.2 (2x), 128.1, 126.6 (2x),
122.9, 120.6, 116.5, 72.7, 69.6, 27.7, 21.5.
Gram-Scale Synthesis of Compound 8. Amberlyst® 15 (A-15,
2.58 g) was added to a solution of 5p (3.42 g, 10 mmol) in
o
toluene (200 mL) at 25 C. The reaction mixture was stirred at
o
25 C for 10 min under Dean-Stark distillation apparatus. 6f
o
(1.12 g, 11 mmol) was added to the reaction mixture at 25 C.
2-Phenylchroman-4-one (11). Freshly prepared Na(Hg)
(~6%, 1 g) was added to a solution of 10 (110 mg, 0.3 mmol)
in MeOH (10 mL) at 25 oC. The reaction mixture was stirred at
The reaction mixture was stirred at reflux for 10 h. The reac-
tion was monitored by TLC. The reaction mixture was cooled
to 25 C. A-15 was filtered by filter paper and the A-15 was
o
o
25 C for 2 h. Mercury was filtered by filter paper and the
washed with toluene (3 x 20 mL). The combined toluene layers
were concentrated. The residue was diluted with saturated
NaHCO3(aq) (30 mL) and the mixture was extracted with EtOAc
(3 x 50 mL). The combined organic layers were washed with
brine (2 x 10 mL), dried (MgSO4), filtered and evaporated to
afford crude product under reduced pressure. The remaining
mixture was separated by column chromatography (silica gel,
hexanes/EtOAc = 8/1~4/1 as eluent) affording 4ah (3.66 g,
85%). Next, NaBH4 (570 mg, 15 mmol) was added to a solu-
tion of 4ah (3.66 g, 8.5 mmol) in THF and MeOH (v/v =1/1,
100 mL) at 25 oC. The reaction mixture was stirred at 25 oC for
fitrates were concentrated. The residue was diluted with satu-
rated NaHCO3(aq) (10 mL) and the mixture was extracted with
CH2Cl2 (3 x 20 mL). The combined organic layers were
washed with brine (2 x 10 mL), dried (MgSO4), filtered and
evaporated to afford crude product under reduced pressure.
Without further purification, PDC (380 mg, 1.0 mmol) was
added to a solution of the resulting crude products in DMF (5
mL) at 25 oC. The reaction mixture was stirred at reflux for 2 h.
The reaction mixture was filterated, washed with CH2Cl2 (3 x
20 mL), and the fitrates were concentrated. The remaining mix-
ture was separated by column chromatography (silica gel, hex-
anes/EtOAc = 10/1~4/1 as eluent) affording 11. Yield = 52%
o
2 h. The reaction mixture was cooled to 25 C and the solvent
was concentrated. The residue was diluted with water (30 mL)
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The Journal of Organic Chemistry
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and the mixture was extracted with CH2Cl2 (3 x 50 mL). The
Corresponding Author
combined organic layers were washed with brine (2 x 10 mL),
dried (MgSO4), filtered and evaporated to afford crude product
under reduced pressure. Without further purification, A-15 (3.0
g) was added to a solution of the resulting crude products in a
3
4
5
6
7
8
9
*Email: mychang@kmu.edu.tw
*Email: hychen@kmu.edu.tw
ORCID
o
toluene (150 mL) at 25 C. The reaction mixture was stirred at
Meng-Yang Chang: 0000-0002-1983-8570
Hsing-Yin Chen: 0000-0003-3948-8915
Notes
reflux for 40 h under Dean-Stark distillation apparatus. The
reaction was monitored by TLC. A-15 was filtered by filter
paper and the A-15 was washed with toluene (3 x 20 mL). The
combined organic layers were concentrated. The residue was
diluted with saturated NaHCO3(aq) (30 mL) and the mixture was
extracted with CH2Cl2 (3 x 50 mL). The combined organic
layers were washed with brine (2 x 10 mL), dried (MgSO4),
filtered and evaporated to afford crude product under reduced
pressure. The remaining mixture was separated by column
chromatography (silica gel, hexanes/EtOAc = 8/1~4/1 as eluent)
affording 2ah (2.55 g, 72%). Finally, freshly prepared Na(Hg)
(~6%, 8 g) was added to a solution of 2ah (2.55 g, 6.1 mmol)
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The authors declare no competing financial interest.
ACKNOWLEDGMENT
The authors would like to thank the Ministry of Science and Tech-
nology of the Republic of China for financial support (MOST 106-
2628-M-037-001-MY3).
REFERENCES
o
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in MeOH (100 mL) at 25 C. The reaction mixture was stirred
o
at 25 C for 6 h. Mercury was filtered by filter paper and the
fitrates were concentrated. The residue was diluted with satu-
rated NaHCO3(aq) (30 mL) and the mixture was extracted with
CH2Cl2 (3 x 50 mL). The combined organic layers were
washed with brine, dried, filtered and evaporated to afford
crude products under reduced pressure. Without further purifi-
cation, PDC (9.4 g, 25 mmol) was added to a solution of the
o
resulting crude products in DMF (60 mL) at 25 C. The reac-
tion mixture was stirred at reflux for 8 h. The reaction mixture
was filterated, washed with CH2Cl2 (3 x 100 mL), and the
fitrates were concentrated. The remaining mixture was separat-
ed by column chromatography (silica gel, hexanes/EtOAc =
8/1~4/1 as eluent) affording 8 (995 mg, 59% of two steps).
DFT calculations. All calculations were carried out with the
Gaussian 09 program.49 The combination of pure functional
M06L with Def2-SVP basis sets was adopted for gas-phase
geometry optimizations and vibrational frequency calculations.
Density fitting approximation50 using W06 fitting set was ex-
ploited to speed up the calculations. To properly model the
dispersion force, the D3 version of Grimme’s empirical disper-
sion correction51 was added in the calculations. Single point
energy calculations with hybrid functional M06-2X and Def2-
TZVP basis sets were performed to provide more accurate en-
ergies. The solvent effect (solvent = THF) was taken into ac-
count in the single point energy calculations by using the SMD
continuum solvation model. Numerical integration was done
with the setting of ultrafine grid. Thermal correction to Gibbs
free energy was made at the standard conditions of 298.15 K
and 1 atm. The natural steric analysis52 was carried out by us-
ing the NBO 6.0 program.53
ASSOCIATED CONTENT
Supporting Information
Scanned photocopies of NMR spectral data for all compounds,
DFT theoretical calculations data and X-ray analysis data of 1a,
1e, 1h, 1q, 1z, 2e, 2g, 2k, 2r, 2ai, 4n, 7l and 9. This infor-
mation is available free of charge via the Internet at http:
//pubs.acs.org.
AUTHOR INFORMATION
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