Synthesis of 2-alkoxyaryl-2-aryl enamines via tandem copper-catalyzed cycloaddition and rhodium-catalyzed alkoxyarylation from alkynes, N -sulfonyl azides, and aryl ethers

Article abstract of DOI:10.1021/acs.joc.5b00891

A synthetic route to a wide range of 2-alkoxyaryl-2-aryl enamines is developed from Rh-catalyzed alkoxyarylation of N-sulfonyl-4-aryl-1,2,3-triazoles with aryl ethers via the elimination of nitrogen molecule. In addition, 2-alkoxyaryl-2-aryl enamines are

Full text of DOI:10.1021/acs.joc.5b00891

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Article
Synthesis of 2-Alkoxyaryl-2-aryl Enamines via Tandem
Copper-Catalyzed Cycloaddition and Rhodium-Catalyzed
Alkoxyarylation from Alkynes, N-Sulfonyl Azides, and Aryl Ethers
Seohyun Shin, Youngchul Park, Cheol-Eui Kim, Jeong-Yu Son, and Phil Ho Lee
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.5b00891 • Publication Date (Web): 05 May 2015
Downloaded from http://pubs.acs.org on May 11, 2015
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Synthesis of 2-Alkoxyaryl-2-aryl Enamines via Tandem Copper-Catalyzed Cycloaddition and
Rhodium-Catalyzed Alkoxyarylation from Alkynes, N-Sulfonyl Azides, and Aryl Ethers
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Seohyun Shin,† Youngchul Park,† CheolꢀEui Kim, JeongꢀYu Son, and Phil Ho Lee*
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National Creative Research Initiative Center for Catalytic Organic Reactions, Department of
Chemistry, Kangwon National University, Chuncheon 200ꢀ701, Republic of Korea
Eꢀmail: phlee@kangwon.ac.kr
Table of Contents
ABSTRACT A synthetic route to a wide range of 2ꢀalkoxyarylꢀ2ꢀaryl enamines is developed from
Rhꢀcatalyzed alkoxyarylation of Nꢀsulfonylꢀ4ꢀarylꢀ1,2,3ꢀtriazoles with aryl ethers via the
elimination of nitrogen molecule. In addition, 2ꢀalkoxyarylꢀ2ꢀaryl enamines are prepared via
tandem Cuꢀcatalyzed cycloaddition and Rhꢀcatalyzed alkoxyarylation starting from alkynes, Nꢀ
sulfonyl azides, and aryl ethers in oneꢀpot.
INTRODUCTION
NꢀSulfonylꢀ1,2,3ꢀtriazoles obtained from Cuꢀcatalyzed cycloaddition reaction of terminal alkynes
with Nꢀsulfonyl azides1 have received considerable attention and have proven to be highly effective
as precursors of αꢀimino rhodium carbenes.2 Because in situ generated αꢀimino rhodium carbenes
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are a kind of electrophiles, reactions of the carbenes with a wide range of nucleophiles have been
examined and a variety of heterocyclic compounds have been prepared.3 In this regard, we also
have demonstrated the utility of Nꢀsulfonylꢀ1,2,3ꢀtriazoles in the reaction with diene, 2Hꢀazirine, 2ꢀ
ethynylbiaryl, alkenyl ether, and oxacycloalkene.4 Besides Rhꢀcatalyzed intermolecular arylation
using αꢀimino rhodium carbenes is highly attractive because transition metalꢀcatalyzed insertion
reaction of carbenes to aromatic C−H bonds is one of the useful methods in organic synthesis.5 To
date, Rhꢀcatalyzed arylation of αꢀimino Rhꢀcarbenes with boronic acids (eq 1)6 and N,Nꢀ
dialkylanilines (eq 2)7 were reported (Scheme 1). Recently, we have described an efficient Rhꢀ
catalyzed arylation of azulene, which is nonꢀbenzenoid aromatic compound, with Nꢀsulfonylꢀ1,2,3ꢀ
triazoles (eq 3).8 In continuing studies, we envisioned that anisole derivatives which are less
nucleophilic than aniline derivatives would be reacted with αꢀimino rhodium carbenes, leading to
the formation of 2ꢀalkoxyarylꢀ2ꢀaryl enamines. However, the fact that αꢀimino rhodium carbenes
did not react with anisole7 or 1,2ꢀdimethoxybenzene9 was recently reported by Murakami and
Anbarasan group, respectively. These results stimulated us to investigate intensively the feasibility
of aryl ether derivatives as nucleophile in the reaction with αꢀimino rhodium carbenes. In addition,
because 2ꢀalkoxyarylꢀ2ꢀaryl amines were found in biologically active compounds, particularly in
the mammalian hormone thyroxine (Figure 1),10 Rhꢀcatalyzed insertion reaction of αꢀimino
rhodium carbenes with aromatic C−H bonds on aryl ethers would be highly desirable. Herein, we
report a synthetic method to a wide range of 2ꢀalkoxyarylꢀ2ꢀaryl enamines from Rhꢀcatalyzed
insertion reaction of Nꢀsulfonylꢀ4ꢀarylꢀ1,2,3ꢀtriazoles with aryl ethers. In addition, 2ꢀalkoxyarylꢀ2ꢀ
aryl enamines are prepared via tandem Cuꢀcatalyzed cycloaddition and Rhꢀcatalyzed
alkoxyarylation starting from alkynes, Nꢀsulfonyl azides, and aryl ethers in oneꢀpot. These results
overcome the previous synthetic problems and limitation.
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Scheme 1. Rh-Catalyzed Intermolecular Reactions of N-Sulfonyl-1,2,3-triazoles with Aromatic
Compounds.
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R4
(eq 1)
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NHSO2R2
R1
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B(OH)2
Fokin
R4
OR3
NR3
2
OR3
NR3
2
R4
this work
R4
N
N
NSO2R2
R4
R4
NHSO2R2
(eq 2)
(eq 4)
R1
Anbarasan
NHSO2R2
R1
R1
R4
Lee
R4
(eq 3)
NHSO2R2
R1
Figure 1. 2-Alkoxyaryl-2-aryl Ethyl Amine Scaffold in Biologically Active Compounds
(Mammalian Hormone Thyroxine)
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RESULTS AND DISCUSSION
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The initial experiment was carried out with Nꢀtosylꢀ4ꢀphenylꢀ1,2,3ꢀtriazole (1a) and anisole (2a)
in the presence of rhodium(II) catalyst (Table 1). When 1a (0.2 mmol) was treated with 2a (3 equiv)
in the presence of Rh2(OAc)4 (1.0 mol %) in dichloromethane (1 mL) at 70 oC for 18 h, the desired
2ꢀ(4ꢀmethoxyphenyl)ꢀ2ꢀphenyl enamine 3aa was obtained via selective arylation at paraꢀposition
albeit low yield (13%) along with the recovery of 1a (43%) (entry 1). Although the amount of
anisole was increased by up to 10 equivalents due to its low boiling point, the product yield was not
largely increased (entries 2 and 3). For this reason, anisole was employed to this reaction as not
only reagent but also solvent and yield of 3aa was increased to 28% (entry 4). Next, a broad range
of rhodium(II) catalysts such as Rh2(Oct)4, Rh2(Piv)4, Rh2(SꢀDOSP)4, Rh2(SꢀPTAD)4, and Rh2(esp)2
were examined to disclose that Rh2(esp)2 (1.0 mol %) was the catalyst of choice (entries 5ꢀ9).
Changing the temperature to 60ꢀ120 oC had an effect on the yield of the product 3aa (entries 10ꢀ13).
After Rh2(esp)2 was identified as the optimal catalyst, the reactions to determine reasonable
amounts of anisole were examined. Likewise, use of anisole (46 equiv) gave the superior yield to
one of anisole (5 and 10 equiv) (entries 14 and 15). The optimal condition was realized from a
reaction of 1a (0.2 mmol) with 2a (46 equiv) using Rh2(esp)2 (1.0 mol %) at 100 °C for 1.5 h,
furnishing 3aa in 82% isolated yield (entry 12). No any ortho arylated compound was observed. To
show the practicability of this method to largerꢀscale processes, 1.0 and 2.0 mmol scale of triazole
1a was treated with anisole 2a (46 equiv) under the optimal conditions, leading to the formation of
the desired product 3aa in 77% and 70% yields, respectively (entries 16 and 17).
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Table 1. Reaction Optimizationa
3
4
OMe
5
6
7
8
OMe
N
N
cat.
- N2
NTs
+
Ph
NHTs
Ph
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1a
2a
temp (oC)
3aa
yield (%)b
entry cat. (1.0 mol %)
time (h)
1c
2d
3e
70
18
18
18
13 (43)f
15 (35)f
16 (32)f
Rh2(OAc)4
Rh2(OAc)4
70
70
70
70
Rh2(OAc)4
Rh2(OAc)4
4
18
5
28 (30)f
Rh2(Oct)4
Rh2(Piv)4
5
6
41
70
2
50
Rh2(S-DOSP)4
Rh2(S-PTAD)4
Rh2(esp)2
7
8
9
70
70
70
5
48
40
57
7
4.5
Rh2(esp)2
Rh2(esp)2
10
11
60
80
5
43
58
84 (82)g
1.5
Rh2(esp)2
Rh2(esp)2
Rh2(esp)2
Rh2(esp)2
12
100
120
100
100
1.5
1
13
78
14d
15e
16h
17i
3.5
3
40
47
Rh2(esp)2
Rh2(esp)2
100
100
1.5
1.5
77g
70g
aReactions were carried out with Nꢀtosylꢀ4ꢀphenylꢀ1,2,3ꢀtriazole 1a (0.2 mmol) and anisole 2a (46
b
c
equiv). NMR yield using CH2Br2 as an internal standard. 2a (3 equiv) was used in DCE (1 mL).
d2a (5 equiv) was used in DCE (1 mL). e2a (10 equiv) was used in DCE (1 mL). fRecovered yield of
g
h
i
1a. Isolated yield. 1a (1 mmol) and 2a (46 equiv) was used. 1a (2 mmol) and 2a (46 equiv) was
used.
Next, we investigated the effect of the R substituent on the sulfonyl group, which did not
influence the efficiency of the reaction (Scheme 2). The alkoxyarylation reaction was amenable
with respect to methyl, pꢀtolyl, 4ꢀmethoxyphenyl, and 4ꢀtrifluoromethylphenyl to afford the
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products 3aaꢀ3da in good yields ranging from 73% to 82%. The scope of this reaction is
considerably widespread. Electronꢀdonating methyl and methoxy groups on the phenyl ring were
subjected to the Rhꢀcatalyzed alkoxyarylation reactions, producing the desired 2ꢀ(4ꢀ
methoxyphenyl)ꢀ2ꢀphenyl enamines (3ea, 3fa, 3ga, 3ha, and 3ia) in good to excellent yields
ranging from 80% to 90%. The reactions of triazole 1 with electronꢀwithdrawing chloro and bromo
groups on the phenyl ring afforded the 4ꢀmethoxyarylated products (3ja, 3ka, and 3la) in good
yields. The tolerance of these halide groups is significant, as additional transformations of the
functional groups are practicable. Trifluoromethyl and nitro substituted triazoles are applicable to
the present transformation, providing the corresponding 2ꢀ(4ꢀmethoxyphenyl)ꢀ2ꢀphenyl enamines
(3ma and 3na). When 2ꢀnaphthyl substituted triazole 1o was employed, the desired enamine 3oa
was obtained in 80% yield. It was noted that thiophenꢀ3ꢀyl substituted triazole were applied to the
present Rhꢀcatalyzed arylation reaction, furnishing 3pa in 60% yield. To our delight, the catalytic 4ꢀ
methoxyphenylation using 4,5ꢀdisubstituted triazole 1q took place to give 3qa in 70% yield.
However, Nꢀtosylꢀ1,2,3ꢀtriazoles having alkyl substituents such as nꢀBu, tꢀBu, and cyclohexenꢀ1ꢀyl
at 4ꢀposition was not arylated with anisole.
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Scheme 2. Scope of Triazolesa
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8
OMe
OMe
N
N
Rh2(esp)2 (1.0 mol %)
NSO2R
+
100 oC, 1.5 h
- N2
Ar
NHSO2R
OMe
9
Ar
1
2a
3
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OMe
R = Me 73% 3ba
C6H4-4-Me 82% 3aa
C6H4-4-OMe 81% 3ca
C6H4-4-CF3 79% 3da
NHSO2R
Me
NHTs
88% 3ea
OMe
OMe
OMe
OMe
NHTs
NHTs
NHTs
NHTs
Me
OMe
MeO
80% 3ha
80% 3fa
80% 3ga
90% 3ia
MeO
OMe
OMe
OMe
OMe
NHTs
NHTs
NHTs
Cl
NHTs
F3C
Cl
Br
84% 3ja
86% 3ka
76% 3la
80% 3ma
OMe
OMe
OMe
OMe
NHTs
NHTs
NHTs
NHTs
O2N
S
87% 3na
3oa
3pa
60%
80%
70%
3qa
aReactions were carried out with 1 (0.2 mmol) and 2a (46 equiv) at 100 oC for 1 ꢀ 1.5 h.
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Encouraged by these results, we next turned our attention to the scope and functional group
tolerance of this rhodiumꢀcatalyzed regioselective alkoxyarylation reaction of triazoles 1 by
variation of the aryl ethers 2 (Scheme 3). Reaction of Nꢀtosyl 4ꢀphenylꢀ1,2,3ꢀtriazole (1a) with ethyl
phenyl ether (2b) gave the desired 4ꢀethoxyphenylation product 4ab in 71% yield. Diphenyl ether
(2c) also worked, leading to the corresponding enamine 4ac in 82% yield without the formation of
diarylated one. 4ꢀMethoxyphenyl phenyl ether (2d) turned out to be compatible with the reaction
conditions, furnishing 4ad in 80% yield. No any ortho arylated products were detected. The ortho
arylation product was not produced even if 4ꢀmethylanisole blocked with methyl group was used. 3ꢀ
Methylanisole and 1,2ꢀ and 1,3ꢀdimethoxybenzene are applicable to the present arylation,
selectively providing the desired enamines (4ae, 4af, and 4ag) in good yields. Both 2,3ꢀ
dihydrobenzofuran (2h) and 1,3ꢀbenzodioxole (2i) were regioselectively transformed to the arylated
products 4ah (65%) and 4ai (70%). 1ꢀMethoxynaphthalene (2j) was successfully arylated to deliver
the enamine 4aj in 80% yield. When 1,2,5ꢀtrimethoxybenzene (2k) underwent the arylation under
the optimal conditions, the desired enamine 4ak was obtained in 71% yield. In the case of 1,3,5ꢀ
trimethoxybenzene, the desired product 4al was produced in 53% yield with 2.0 mol % of Rh
catalyst due to the steric hindrance. The substrate (2m) having triple bond worked equally well in
the reaction with triazole to provide the corresponding enamine 4am in 88% yield. 4ꢀBromobutyl
phenyl ether (2n) was also readily employed in the arylation reaction. Delightedly, diphenyl ether
(2c), 1,3ꢀdimethoxybenzene (2g), and 2,3ꢀdihydrobenzofuran (2h) reacted smoothly with 2ꢀ
bromophenyl substituted triazole (1l) to give the corresponding enamines (4lc, 4lg, and 4lh) in
moderate to good yields ranging from 57% to 90%.
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Scheme 3. Scope of Aryl Ethersa
3
4
5
6
7
8
9
OR1
OR1
N
Rh2(esp)2 (1.0 mol %)
N
R2
NTs
+
100 oC
- N2
R2
Ar
NHTs
Ar
1
2
4
10
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OMe
OEt
O
O
OMe
Me
NHTs
NHTs
NHTs
NHTs
Ph
Ph
Ph
Ph
71% 4ab
82% 4ac
80% 4ad
70% 4ae
OMe
OMe
O
O
O
OMe
MeO
NHTs
NHTs
73% 4af
NHTs
NHTs
Ph
Ph
Ph
Ph
65%b 4ah
70% 4ai
77% 4ag
Et
OMe
OMe
OMe
OMe
OMe
MeO
OMe
NHTs
O
MeO
Ph
NHTs
NHTs
NHTs
Ph
Ph
53%b
Ph
88% 4am
80% 4aj
4al
71% 4ak
OPh
OMe
O
Br
O
MeO
NHTs
NHTs
NHTs
NHTs
Ph
Br
Br
Br
90% 4lg
70% 4an
65% 4lc
57% 4lh
aReactions were carried out with 1a (0.2 mmol) and 2 (46 equiv) at 100 oC for 1 ꢀ 1.5 h. b2.0 mol %
Rh2(esp)2 was used.
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3ꢀMethoxyphenyl substituted triazole 5 was intramolecularly cyclized in the presence of 1.0
mol % Rh2(esp)2 in xylene, regioselectively producing paraꢀarylated product 6 in 50% yield (eq 5).
5
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A threeꢀcomponent oneꢀpot synthesis of 2ꢀ(4ꢀalkoxyaryl)ꢀ2ꢀaryl enamines 3 and 4 starting from
terminal alkynes, tosyl azide, and aryl ethers was conducted to demonstrate the synthetic utility of
the Rhꢀcatalyzed alkoxyarylation reaction (Table 2). Placing a wide range of substituents such as
methyl, methoxy, chloro, and nitro on the aryl group of arylacetylenes and methyl and phenyl group
on the aryl ethers have little effect on the reaction results and affords the corresponding 2ꢀ
(alkoxyaryl)ꢀ2ꢀaryl enamines in good yields ranging from 50% to 67% in oneꢀpot.
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Table 2. Alkoxyarylation in One-Pota
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o
aReactions were carried out with 7 (0.2 mmol), 8 (0.2 mmol), and 2 (46 equiv) (25 C for 2 h and
then, 100 oC for 1.5 h).
When the 2ꢀ(4ꢀalkoxyaryl)ꢀ2ꢀphenyl enamines 3 and 4 were treated with NaBH3CN in toluene
at 80 oC for 8 h, reductive reaction smoothly took place to afford 2ꢀ(4ꢀalkoxyaryl)ꢀ2ꢀphenyl amines
9 in good yields ranging from 62% to 86% (eq 6).
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A variety of indoles (10) having alkoxyaryl moieties at 3ꢀposition were produced via
intramolecular crossꢀcoupling reactions of 2ꢀbromophenyl substituted enamines 4 using CuI (5 mol
%), DMEDA (10 mol %), and K3PO4 (2 equiv) in toluene at 75 °C for 4 h (eq 7).7,11
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A plausible mechanism for the present alkoxyarylation is illustrated in Scheme 4. Nucleophilic
addition of aryl ethers 2 to the αꢀimino rhodium(II) carbenoid B derived from triazoles 1 leads to
the rhodiumꢀbound zwitterionic intermediate C, which is converted to the corresponding 2ꢀ
alkoxyarylꢀ2ꢀaryl enamines 3 and 4. Because the cyclopropyl aldimine D generated from [2 + 1]
cycloaddition of B with 2 are not observable, the intermediate D is ruled out in the catalytic cycle.
This is supported by the fact that the dihydropyrrole E via Clock rearrangement and
cycloheptatriene F via Büchner reaction which might be produced from D are not detected.
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Scheme 4. A Proposed Mechanism
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OR1
N2
[Rh2L4]
NTs
N
Ar
N
A
R2
NTs
7
Ar
8
9
1
3, 4
N2
NTs
Ar
OR1
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Cu(l) [3 + 2]
[Rh]
R2
NTs
TsN3
+
Ar
8
Ar
B
H
NTs
7
OR1
Ar
C
[Rh]
R2
2
[2 + 1]
X
OR1
OR1
R1O
R2
R2
Buchner
reaction
Clock
rearrangement
R2
TsN
Ar
Ar
Ar
TsN
TsN
E
D
F
not observed
CONCLUSION
In summary, an efficient synthetic method to a myriad of 2ꢀalkoxyarylꢀ2ꢀaryl enamines is
developed from Rhꢀcatalyzed alkoxyarylation of Nꢀsulfonylꢀ4ꢀarylꢀ1,2,3ꢀtriazoles with aryl ethers
via the elimination of nitrogen molecule. Cuꢀcatalyzed cycloaddition followed by Rhꢀcatalyzed
alkoxyarylation starting from alkynes, Nꢀsulfonyl azides, and aryl ethers is also demonstrated for
synthesis of 2ꢀalkoxyarylꢀ2ꢀaryl enamines in oneꢀpot. These results overcome the previous synthetic
problems and limitation.
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Experimental Section
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General: Reactions were carried out in ovenꢀdried glassware under N2 condition. Rh2(OAc)4,
Rh2(esp)2, Rh2(Piv)4, Rh2(Oct)4, Rh2(SꢀPTAD)4, and Rh2(SꢀDOSP)4 were purchased. Commercial
available reagents were used without purification. All reaction mixtures were stirred magnetically
and were monitored by thinꢀlayer chromatography using silica gel precoated glass plates, which
were visualized with UV light and then, developed using either iodine or a solution of anisaldehyde.
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Flash column chromatography was carried out using silica gel (230− 400 mesh). H NMR (400
MHz), 13C{1H} NMR (100 MHz) spectra were recorded on NMR spectrometer. Deuterated
chloroform was used as the solvent and chemical shift values (δ) are reported in parts per million
1
relative to the residual signals of this solvent [δ 7.26 for H (chloroformꢀd), δ 77.2 for 13C{1H}
(chloroformꢀd). Infrared spectra were recorded on FTꢀIR spectrometer as either a thin film pressed
between two sodium chloride plates or as a solid suspended in a potassium bromide disk. High
resolution mass spectra (HRMS) were obtained by fast atom bombardment (FAB) using a double
focusing magnetic sector mass spectrometer and electron impact (EI) ionization technique
(magnetic sector ꢀ electric sector double focusing mass analyzer). Melting points were determined
in open capillary tube.
Synthetic procedure of 2,2-diaryl enamines via Rh-catalyzed arylation of triazole derivative
with aryl ether: Rh2(esp)2 (1.52 mg, 0.002 mmol) and triazole derivative (1, 0.2 mmol)1b,12 were
added to an dried test tube equipped with stir bar under nitrogen atmosphere. Subsequently, aryl
o
ether (2, 46 equiv) was added through syringe. The mixture was stirred at 100 C for 1h, at which
time triazole was completely comsumed on TLC. Then, the reaction mixture was cooled to
ambinent temperature and silica gel column chromatography (EtOAc:hexane) gave 2,2ꢀdiaryl
enamines.
Synthetic procedure of 2,2-diaryl enamines via Cu-catalyzed [3+2] cycloaddition and Rh-
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catalyzed arylation of alkyne, tosyl azide and aryl ether in one-pot: A mixture of CuTC (3.8 mg,
0.02 mmol), Rh2(esp)2 (1.52 mg, 0.002 mmol), acetylene (7, 1 equiv) and tosyl azide (8, 1 equiv)
were added to an ovenꢀdried test tube equipped with a stir bar under nitrogen atmosphere.
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Subsequently, aryl ether (2, 46 equiv) was added through syringe. The mixture was stirred at 25 C
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for 2 h and then, the mixture was stirred for 1.5 h at 100 C. After the mixture was cooled to
ambinet temperature and silica gel column chromatopraphy (EtOAc:hexane) gave 2,2ꢀdiaryl
enamines.
N-(2-(4-Methoxyphenyl)-2-phenylvinyl)-4-methylbenzenesulfonamide (3aa) : 62.2 mg (82%),
1
Rf = 0.4 (EtOAc:hexane = 1:3); pale yellow oil; E/Z ratio 1.43:1; H NMR (400 MHz, CDCl3) data
for the major isomer;
δ 7.72 (app d, J = 8.3 Hz, 2H), 7.33 (app d, J = 8.0 Hz, 2H), 7.35ꢀ7.30 (m,
1H), 7.26ꢀ7.20 (m, 2H), 7.10 (app d, J = 8.0 Hz, 2H), 6.89ꢀ6.82 (m, 4H), 6.76 (d, J = 11.1 Hz, 1H),
6.30 (d, J = 11.4 Hz, 1H), 3.82 (s, 3H), 2.45 (s, 3H); data for the minor isomer; 7.71 (app d, J = 8.2
Hz, 2H), 7.35ꢀ7.30 (m, 3H), 7.26ꢀ7.20 (m, 2H), 7.02 (app d, J = 8.7 Hz, 2H), 6.89ꢀ6.82 (m, 2H),
6.78 (app d, J = 8.9 Hz, 2H), 6.68 (d, J = 11.5 Hz, 1H), 6.22 (d, J = 11.4 Hz, 1H), 3.77 (s, 3H), 2.45
(s, 3H); 13C{1H} NMR (100 MHz, CDCl3)
δ 159.3, 158.9, 144.0, 143.9, 139.7, 136.8, 136.7, 136.6,
132.1, 130.8, 129.95, 129.93, 129.5, 129.3, 128.4, 128.3, 128.1, 127.8, 127.0, 126.83, 126.81, 126.5,
126.2, 125.9, 120.0, 118.8, 114.8, 113.8, 55.35, 55.32, 21.6; IR (film): 3271, 2956, 1606, 1335,
1161, 832 cmꢀ1; HRMS (EI): m/z calcd for C22H21NO3S : 379.1242; found : 379.1241.
N-(2-(4-Methoxyphenyl)-2-phenylvinyl)methanesulfonamide (3ba) : 44.2 mg (73%), Rf = 0.3
o
1
(EtOAc:hexane = 1:3); white solid; mp 127.2ꢀ130.2 C; E/Z ratio 1.33:1; H NMR (400 MHz,
CDCl3) data for the major isomer; 7.30ꢀ7.24 (m, 1H), 7.23ꢀ7.21 (m, 2H), 7.19ꢀ7.17 (m, 2H), 7.16ꢀ
δ
7.13 (m, 2H), 7.00ꢀ6.97 (m, 2h), 6.77 (d, J = 11.3 Hz, 1H), 6.28 (d, J = 11.3 Hz, 1H), 3.86 (s, 3H),
3.06 (s, 3H); data for the minor isomer; 7.47ꢀ7.43 (m, 2H), 7.40ꢀ7.36 (m, 1H), 7.30ꢀ7.24 (m, 2H),
7.12ꢀ7.09 (m, 2H), 6.83ꢀ6.80 (m, 2H), 6.70 (d, J = 11.4 Hz, 1H), 6.21 (d, J = 11.2 Hz, 1H), 3.79 (s,
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3H), 3.05 (s, 3H); 13C{1H} NMR (100 MHz, CDCl3)
δ
159.5, 158.9, 139.6, 136.7, 131.9, 130.9,
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129.6, 128.5, 128.4, 128.3, 127.8, 127.1, 126.5, 125.2, 124.9, 119.8, 118.6, 115.0, 113.9, 55.4, 55.3,
41.2, 41.1; IR (film): 3278, 3029, 2933, 1512, 1349, 1161, 977, 834 cmꢀ1; HRMS (EI): m/z calcd for
C16H17NO3S : 303.0929; found : 303.0928.
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N-(2-(4-Methoxyphenyl)-2-phenylvinyl)propane-2-sulfonamide (3ca) : 64.0 mg (81%), Rf =
1
0.35 (EtOAc:hexane = 1:3); pale yellow oil; E/Z ratio 2:1; H NMR (400 MHz, CDCl3), data for
the major isomer;
δ 7.79ꢀ7.74 (m, 2H), 7.35ꢀ7.30 (m, 1H), 7.26ꢀ7.18 (m, 2H), 7.11ꢀ7.10 (m, 2H),
6.90ꢀ.6.84 (m, 3H), 6.83ꢀ6.79 (m, 1H), 6.76 (d, J = 11.8 Hz, 1H), 6.28 (d, J = 11.6 Hz, 1H), 3.88 (s,
3H), 3.82 (s, 3H); data for the minor isomer; 7.79ꢀ7.74 (m, 2H), 7.35ꢀ7.30 (m, 2H), 7.26ꢀ7.18 (m,
2H), 7.04ꢀ6.99 (m, 4H), 6.90ꢀ6.84 (m, 3H), 6.68 (d, J = 11.6 Hz, 1H), 6.20 (d, J = 11.6 Hz, 1H),
3.88 (s, 3H), 3.77 (s, 3H); 13C{1H} NMR (100 MHz, CDCl3)
δ 163.2, 159.4, 158.9, 139.7, 136.6,
132.2, 132.1, 131.3, 131.2, 130.8, 129.6, 129.4, 129.0, 128.9, 128.9, 128.1, 127.8, 127.1, 126.6,
126.2, 125.9, 120.1, 118.9, 114.8, 114.5, 114.4, 113.8, 55.7, 55.4, 55.3; IR (film): 3243, 3061, 1691,
1595, 1351, 1259, 1160 cmꢀ1; HRMS (EI): m/z calcd for C22H21NO4S : 395.1191; found : 395.1194.
N-(2-(4-Methoxyphenyl)-2-phenylvinyl)-4-(trifluoromethyl)benzenesulfonamide (3da) : 68.4
mg (79%), Rf = 0.4 (EtOAc:hexane = 1:3); green oil; E/Z ratio 1.2:1; 1H NMR (400 MHz, CDCl3),
data for the major isomer;
δ 7.97 (d, J = 8.2 Hz, 2H), 7.82 (d, J = 8.2 Hz, 2H), 7.36ꢀ7.33 (m, 2H),
7.25ꢀ7.22 (m, 2H), 7.12ꢀ7.10 (m, 2H), 6.90ꢀ6.82 (m, 3H), 6.76 (d, J = 11.4 Hz, 1H), 6.38 (d, J =
11.4 Hz, 1H), 3.83 (s, 3H); data for the minor isomer; 7.96 (d, J = 8.0 Hz, 2H), 7.82 (d, J = 8.2 Hz,
2H), 7.36ꢀ7.33 (m, 1H), 7.03 (dt, J = 9.8, 2.6 Hz, 2H), 6.90ꢀ6.82 (m, 4H), 6.80 (d, J = 8.9 Hz, 2H),
6.70 (d, J = 11.3 Hz, 1H), 6.29 (d, J = 11.3 Hz, 1H), 3.78 (s, 3H); 13C{1H} NMR (100 MHz,
CDCl3)
δ 159.5, 159.2, 143.1, 143.0, 139.3, 136.3, 134.9, 134.6, 131.6, 130.7, 129.5, 129.3, 128.5,
128.4, 127.8, 127.6 (q, Jcf = 38.6 Hz), 127.4, 127.34, 127.32, 126.6, 126.53 (q, Jcf = 3.3 Hz), 124.5,
119.1, 117.8, 114.9, 113.9, 55.4, 55.3; IR (film): 3261, 3060, 1730, 1650, 1323, 1167, 1130, 840
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cmꢀ1; HRMS (EI): m/z calcd for C22H18F3NO3S : 433.0959; found : 433.0957.
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N-(2-(4-Methoxyphenyl)-2-(m-tolyl)vinyl)-4-methylbenzenesulfonamide (3ea) : 69.2 mg (88%),
Rf = 0.4 (EtOAc:hexane = 1:3); brown oil; E/Z ratio 1:1; 1H NMR (400 MHz, CDCl3) δ 7.73ꢀ7.70
(m, 4H), 7.35ꢀ7.33 (m, 4H), 7.21 (t, J = 7.6 Hz, 1H), 7.12 (t, J = 7.7 Hz, 2H), 6.93 (s, 1H), 6.90ꢀ
6.74 (m, 9H), 6.69ꢀ6.74 (m, 2H), 6.59 (s, 1H), 6.26 (d, J = 11.6 Hz, 1H), 6.18 (d, J = 11.5 Hz, 1H),
3.83 (s, 3H), 3.77 (s, 3H), 2.45 (s, 3H), 2.44 (s, 3H), 2.28 (s, 3H), 2.25 (s, 3H); 13C{1H} NMR (100
MHz, CDCl3) δ 159.3, 158.9, 144.0, 143.9, 139.6, 139.0, 138.0, 136.8, 136.6, 136.4, 132.1, 130.8,
130.0, 129.98, 129.90, 129.2, 128.9, 128.4, 128.3, 127.9, 127.8, 126.85, 126.81, 126.5, 126.0, 123.8,
119.9, 118.8, 114.8, 113.8, 55.38, 55.36, 21.6, 21.47, 21.46; IR (film): 3275, 3053, 1724, 1330,
1169, 1090 cmꢀ1; HRMS (EI): m/z calcd for C23H23NO3S : 393.1399; found : 393.1397.
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N-(2-(4-Methoxyphenyl)-2-(p-tolyl)vinyl)-4-methylbenzenesulfonamide (3fa) : 63.0 mg (80%),
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Rf = 0.4 (EtOAc:hexane = 1:3); pale green oil; E/Z ratio 1.76:1; H NMR (400 MHz, CDCl3), data
for the major isomer; δ 7.71 (d, J = 8.3 Hz, 2H), 7.33 (d, J = 7.9 Hz, 2H), 7.14 (d, J = 7.8 Hz, 1H),
7.06ꢀ7.00 (m, 4H), 6.87ꢀ6.73 (m, 3H), 6.72 (d, J = 11.6 Hz, 1H), 6.24 (d, J = 11.9 Hz, 1H), 3.82 (s,
3H), 2.45 (s, 3H), 2.30 (s, 3H); data for the minor isomer; 7.71 (d, J = 8.3 Hz, 2H), 7.33 (d, J = 7.9
Hz, 2H), 7.14 (d, J = 7.8 Hz, 1H), 7.06ꢀ7.00 M, 2H), 6.87ꢀ6.73 (m, 5H), 6.66 (d, J = 11.5 Hz, 1H),
6.20 (d, J = 11.8 Hz, 1H), 3.77 (s, 3H), 2.45 (s, 3H), 2.36 (s, 3H); 13C{1H} NMR (100 MHz,
CDCl3) δ 159.3, 158.9, 144.0, 143.9, 138.0, 137.0, 136.9, 136.8, 136.7, 136.6, 133.5, 132.2, 130.8,
130.0, 129.95, 129.92, 129.4, 129.1, 128.5, 127.8, 126.83, 126.80, 126.5, 126.2, 126.0, 119.3, 118.6,
114.8, 113.8, 55.34, 55.33, 21.6, 21.2, 21.1; IR (film): 3366, 1915, 1633, 1433, 1260, 1124 cmꢀ1;
HRMS (EI): m/z calcd for C23H23NO3S : 393.1399; found : 393.1400.
N-(2-(2-Methoxyphenyl)-2-(4-methoxyphenyl)vinyl)-4-methylbenzenesulfonamide (3ga) : 65.5
mg (80%), Rf = 0.3 (EtOAc:hexane = 1:3); yellow oil; E/Z ratio 2.5:1; 1H NMR (400 MHz, CDCl3),
data for the major isomer; δ 7.70 (d, J = 8.3 Hz, 2H), 7.34ꢀ7.29 (m, 3H), 7.04 (dt, J = 9.8, 2.6 Hz,
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2H), 6.94ꢀ6.80 (m, 3H), 6.79ꢀ6.71 (m, 3H), 6.15 (d, J = 11.3 Hz, 1H), 3.76 (s, 3H), 3.54 (s, 3H),
2.42 (s, 3H); data for the minor isomer; 7.73 (d, J = 8.3 Hz, 2H), 7.34ꢀ7.29 (m, 2H), 7.20ꢀ7.16 (m,
1H), 6.94ꢀ6.80 (m, 5H), 6.79ꢀ6.72 (m, 3H), 3.80 (s, 3H), 3.67 (s, 3H), 2.44 (s, 3H); 13C{1H} NMR
(100 MHz, CDCl3) δ 158.9, 158.7, 157.3, 156.8, 143.8, 143.7, 137.2, 137.0, 132.0, 131.6, 130.8,
130.6, 130.2, 129.9, 129.8, 129.7, 126.9, 126.8, 126.5, 124.7, 122.8, 122.0, 121.9, 121.4, 120.5,
119.6, 114.5, 111.9, 111.4, 58.1, 55.6, 55.5, 55.3, 21.6, 21.5; IR (film): 3279, 30624 1916, 16421
1351, 1162, 1089 cmꢀ1; HRMS (EI): m/z calcd for C23H23NO4S : 409.1348; found : 409.1347.
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N-(2-(3-Methoxyphenyl)-2-(4-methoxyphenyl)vinyl)-4-methylbenzenesulfonamide (3ha) : 65.5
mg (80%), Rf = 0.3 (EtOAc:hexane = 1:3); brown solid; mp: 148ꢀ151 oC; E/Z ratio 1.25:1; 1H NMR
(400 MHz, CDCl3) data for the major isomer; δ 7.71 (dd, J = 8.3, 1.4 Hz, 2H), 7.34 (d, J = 8.0 Hz,
2H), 7.16 (t, J = 8.0 Hz, 1H), 7.04 (d, J = 8.9 Hz, 1H), 6.88ꢀ6.74 (m, 5H), 6.68 (d, J = 11.6 Hz, 1H),
6.62 (t, J = 2.1 Hz, 1H), 6.27 (d, J = 11.6 Hz, 1H), 3.83 (s, 3H), 3.74 (s, 3H), 2.45 (s, 3H); data for
the minor isomer; 7.71 (dd, J = 8.3, 1.4 Hz, 2H), 7.33 (d, J = 8.0 Hz, 2H), 7.25 (t, J = 7.1 Hz, 1H),
7.04 (d, J = 4.6 Hz, 1H), 6.88ꢀ6.74 (m, 4H), 6.72ꢀ6.69 (m, 1H), 6.46 (dt, J = 7.5, 1.2 Hz), 6.44ꢀ6.43
(m, 1H), 6.26 (d, J = 11.5 Hz, 1H), 3.77 (s, 3H), 3.71 (s, 3H), 2.44 (s, 3H); 13C{1H} NMR (100
MHz, CDCl3) δ 160.3, 159.6, 159.4, 158.9, 144.0, 143.9, 141.2, 137.9, 136.7, 131.8, 130.4, 129.94,
129.91, 129.3, 128.2, 127.7, 126.8, 125.9, 125.7, 121.7, 120.3, 119.1, 118.7, 114.83, 114.80, 113.8,
113.7, 113.5, 112.6, 112.1, 55.3, 55.32, 55.23, 55.2, 21.63, 21.62; IR (film): 3268, 3064, 3001, 2936,
1682, 1635, 1597, 1350, 1161, 1036 cmꢀ1; HRMS (EI): m/z calcd for C23H23NO4S : 409.1348;
found : 409.1346.
N-(2,2-Bis(4-methoxyphenyl)vinyl)-4-methylbenzenesulfonamide (3ia) : 73.6 mg (90%), Rf =
0.3 (EtOAc:hexane = 1:3); yellow oil; 1H NMR (400 MHz, CDCl3) δ 7.71 (d, J = 8.3 Hz, 2H), 7.345
(d, J = 8.0 Hz, 2H), 7.02 (dt, J = 9.9, 2.7 Hz, 2H), 6.86 (dt, J = 9.1, 2.4 Hz, 2H), 6.81ꢀ6.77 (m, 4H),
6.65 (d, J = 11.5 Hz, 1H), 6.22 (d, J = 11.4 Hz, 1H), 3.82 (s, 3H), 3.77 (s, 3H), 2.44 (s, 3H);
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13C{1H} NMR (100 MHz, CDCl3) δ 159.3, 158.9, 143.9, 136.7, 132.3, 132.2, 130.7, 129.9, 128.8,
128.5, 127.7, 126.8, 125.9, 118.5, 114.7, 113.7, 113.4, 55.34, 55.32, 21.6; IR (film): 3337, 2916,
1916, 1730, 1595, 1417, 1121 cmꢀ1; HRMS (EI): m/z calcd for C23H23NO4S : 409.1348; found :
409.1344.
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N-(2-(3-Chlorophenyl)-2-(4-methoxyphenyl)vinyl)-4-methylbenzenesulfonamide (3ja) : 69.4
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mg (84%), Rf = 0.4 (EtOAc:hexane = 1:3); white solid; mp: 58ꢀ65 C; E/Z ratio 1.76:1; H NMR
(400 MHz, CDCl3), data for the major isomer; δ 7.73ꢀ7.30 (m, 2H), 7.35 (d, J = 8.0 Hz, 2H), 7.17ꢀ
7.16 (m, 2H), 7.05ꢀ7.04 (m, 1H), 6.87 (dt, J = 9.2, 2.4 Hz, 2H), 6.84ꢀ6.80 (m, 2H), 6.79ꢀ6.75 (m,
2H), 6.79ꢀ6.75 (m, 2H), 6.33 (d, J = 11.6 Hz, 1H), 3.83 (s, 3H), 2.46 (s, 3H); data for the minor
isomer; 7.73ꢀ7.70 (m, 2H), 7.36 (d, J = 8.0 Hz, 2H), 7.31ꢀ7.27 (m, 2H), 7.01ꢀ6.99 (m, 3H), 6.84ꢀ
6.80 (m, 2H), 6.78ꢀ6.73 (m, 1H), 6.68 (d, J = 11.6 Hz, 1H), 6.16 (d, J = 11.5 Hz, 1H), 3.78 (s, 3H),
2.45 (s, 3H); 13C{1H} NMR (100 MHz, CDCl3) δ 159.5, 159.1, 144.2, 141.7, 138.5, 136.7, 136.4,
135.1, 134.4, 131.4, 130.8, 130.7, 130.1, 130.0, 129.6, 129.5, 128.4, 127.8, 127.7, 127.6, 127.0,
126.8, 126.6, 125.3, 124.6, 124.4, 121.1, 119.4, 116.0, 115.0, 114.8, 113.9, 55.4, 55.3, 21.7; IR
(film): 3263, 3065, 1716, 1635, 1349, 1248, 1164, 736 cmꢀ1; HRMS (EI): m/z calcd for
C22H20ClNO3S : 413.0852; found : 413.0856.
N-(2-(4-Chlorophenyl)-2-(4-methoxyphenyl)vinyl)-4-methylbenzenesulfonamide (3ka) : 71.0
mg (86%), Rf = 0.4 (EtOAc:hexane = 1:3); yellow oil; E/Z ratio 1.67:1; 1H NMR (400 MHz, CDCl3),
data for the major isomer; δ 7.72 (d, J = 8.3 Hz, 2H), 7.35 (d, J = 8.0 Hz, 2H), 7.20 (td, J = 9.1, 2.3
Hz, 2H), 7.04ꢀ6.98 (m, 2H), 6.90ꢀ6.86 (m, 2H), 6.83ꢀ6.78 (m, 2H), 6.74 (d, J = 11.6 Hz, 1H), 6.29
(d, J = 11.6 Hz, 1H), 3.83 (s, 3H), 2.46 (s, 3H); data for the minor isomer; 7.72 (d, J = 8.3 Hz, 2H),
7.35 (d, J = 8.0 Hz, 2H), 7.31 (d, J = 8.4 Hz, 2H), 7.04ꢀ6.98 (m, 2H), 6.83ꢀ6.78 (m, 4H), 6.69 (d,
11.6 Hz, 1H), 6.13 (d, J = 11.6 Hz, 1H), 3.78 (s, 3H), 2.46 (s, 3H); 13C{1H} NMR (100 MHz,
CDCl3) δ 159.5, 159.1, 144.1, 138.3, 136.7, 136.6, 135.1, 134.1, 132.8, 131.7, 131.1, 130.8, 130.0,
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129.6, 128.5, 127.8, 126.8, 126.7, 124.9, 124.6, 120.4, 119.2, 114.9, 113.9, 55.4, 55.3, 21.6; IR
(film): 3261, 3070, 1689, 1632, 1310, 1250, 720 cmꢀ1; HRMS (EI): m/z calcd for C22H20ClNO3S :
413.0852; found : 413.0853.
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N-(2-(2-Bromophenyl)-2-(4-methoxyphenyl)vinyl)-4-methylbenzenesulfonamide (3la) : 69.5
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mg (76%), Rf = 0.4 (EtOAc:hexane = 1:3); white solid; mp: 140ꢀ145 C; E/Z ratio 10:1; H NMR
(400 MHz, CDCl3), data for the major isomer; δ 7.71 (d, J = 8.3 Hz, 2H), 7.62 (dd, J = 8.0, 1.2 Hz,
1H), 7.32ꢀ7.27 (m, 1H), 7.22 (td, J = 11.6, 1.8 Hz, 1H), 7.00 (dt, J = 9.8, 2.6 Hz, 2H), 6.89 (dd, J =
7.5, 1.8 Hz, 1H), 6.82ꢀ6.77 (m, 3H), 5.96 (d, J = 11.6 Hz, 1H), 3.76 (s, 3H), 2.43 (s, 3H); data for
the minor isomer; 7.77 (d, J = 8.4 Hz, 2H), 7.51 (dd, J = 8.0, 1.2 Hz, 1H), 7.40ꢀ7.34 (m, 4H), 7.18ꢀ
7.10 (m, 2H), 6.92ꢀ6.91 (m, 1H), 6.82ꢀ6.77 (m, 2H), 6.68 (d, J = 11.7 Hz, 1H), 6.44 (d, J = 11.6 Hz,
1H), 3.78 (s, 3H), 2.45 (s, 3H); 13C{1H} NMR (100 MHz, CDCl3) δ 159.0, 158.8, 144.1, 144.0,
141.0, 136.9, 136.8, 133.7, 133.3, 132.1, 131.9, 130.3, 130.2, 130.1, 130.0, 129.97, 129.95, 129.90,
129.0, 128.6, 128.3, 127.3, 127.0, 126.8, 124.5, 124.3, 124.1, 124.0, 123.0, 119.8, 114.5, 114.0,
61.4, 55.3, 21.7, 21.6; IR (film): 3266, 3062, 3000, 1715, 1643, 1511, 1165, 560 cmꢀ1; HRMS
(EI): m/z calcd for C22H20BrNO3S : 457.0347; found : 457.0347.
N-(2-(4-Methoxyphenyl)-2-(4-(trifluoromethyl)phenyl)vinyl)-4-methylbenzenesulfonamide
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(3ma) : 71.5 mg (80%), Rf = 0.4 (EtOAc:hexane = 1:3); pale green oil; E/Z ratio 2.3:1; H NMR
(400 MHz, CDCl3), data for the major isomer; δ 7.73 (d, J = 8.3 Hz, 2H), 7.48 (d, J = 8.2 Hz, 2H),
7.35 (d, J = 8.1 Hz, 2H), 7.20 (d, J = 8.1 Hz, 2H), 6.92ꢀ6.77 (m, 5H), 6.41 (d, J = 11.6 Hz, 1H),
3.83 (s, 3H), 2.45 (s, 3H); data for the minor isomer; 7.73 (d, J = 8.3 Hz, 2H), 7.59 (d, J = 8.0 Hz,
2H), 7.35 (d, J = 8.1 Hz, 2H), 7.04 (d, J = 8.0 Hz, 2H), 6.99 (dt, J = 9.7, 2.6 Hz, 2H), 6.91ꢀ6.77 (m,
2H), 6.73 (d, J = 11.6 Hz, 1H), 6.22 (d, J = 11.5 Hz, 1H), 3.78 (s, 3H), 2.46 (s, 3H); 13C{1H} NMR
(100 MHz, CDCl3) δ 159.6, 159.2, 144.3, 143.3, 140.7, 136.7, 136.6, 131.4, 130.8, 130.0, 128.8 (q,
Jcf = 3.8 Hz), 127.9, 127.5, 126.8, 126.7, 126.6, 126.3 (q, Jcf = 3.8 Hz), 125.5, 125.3 (q, Jcf = 3.8 Hz),
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124.6, 124.1, 121.9, 119.7, 115.1, 114.0, 55.37, 55.34, 21.6; IR (film): 3281, 3064, 1702, 1639,
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1324, 1245, 842 cmꢀ1; HRMS (EI): m/z calcd for C23H20F3NO3S : 447.1116; found : 447.1117.
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(87%), Rf = 0.3 (EtOAc:hexane = 1:3); yellow solid; mp 152ꢀ155 C; E/Z ratio 3:1; H NMR (400
MHz, CDCl3), date for the major isomer; δ 8.08 (td, J = 9.5, 2.3 Hz, 2H), 7.73 (d, J = 8.3 Hz, 2H),
7.37 (d, J = 8.0 Hz, 2H), 7.27 (td, J = 9.5, 2.3 Hz, 2H), 7.00ꢀ6.95 (m, 1H), 6.94ꢀ6.85 (m, 4H), 6.51
(d, J = 11.7 Hz, 1H), 3.84 (s. 3H), 2.46 (s, 3H); data for the minor isomer; 8.17 (td, J = 9.2, 2.2 Hz,
2H), 7.73 (d, J = 8.3 Hz, 2H), 7.37 (d, J = 8.6 Hz, 2H), 7.11 (d, J = 9.3, 2.2 Hz, 2H), 7.00ꢀ6.95 (m,
2H), 6.80 (td, J = 9.8, 2.6 Hz, 2H), 6.75 (d, J = 11.6 Hz, 1H), 6.40 (d, J = 11.6 Hz, 1H), 3.79 (s, 3H),
2.47 (s, 3H); 13C{1H} NMR (100 MHz, CDCl3) δ 159.8, 159.3, 147.3, 146.4, 146.3, 144.5, 144.4,
144.0, 136.6, 136.5, 131.2, 130.9, 130.6, 130.1, 130.0, 128.2, 126.8, 126.7, 126.6, 124.5, 123.8,
123.7, 123.6, 123.1, 120.6, 115.3, 114.1, 55.4, 55.3, 21.7; IR (film): 3268, 3074, 3003, 1723, 1593,
1161 cmꢀ1; HRMS (EI): m/z calcd for C22H20N2O5S : 424.1093; found : 424.1093.
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N-(2-(4-Methoxyphenyl)-2-(naphthalen-2-yl)vinyl)-4-methylbenzenesulfonamide (3oa) : 68.7
mg (80%), Rf = 0.4 (EtOAc:hexane = 1:3); yellow oil; E/Z ratio 1.76:1 1H NMR (400 MHz, CDCl3)
δ 7.85ꢀ7.70 (m, 6.5H), 7.69ꢀ7.63 (m, 1.6H), 7.53ꢀ7.50 (m, 1.2H), 7.43ꢀ7.30 (m, 3.7H), 7.37ꢀ7.30 (m,
4.2H), 7.06 (dt, J = 9.8, 2.6 Hz, 1.1H), 6.97 (dd, J = 8.4, 1.7 Hz, 0.6H), 6.92ꢀ6.87 (m, 5H), 6.80ꢀ
6.76 (m, 1.6H), 6.35 (d, J = 11.6 Hz, 0.6H), 3.84 (s, 3H), 3.78 (s, 1.7H), 2.49 (s, 1.7H), 2.45 (s, 3H)
13C{1H} NMR (100 MHz, CDCl3) δ 159.4, 159.0, 144.1, 144.0, 137.0, 136.8, 136.7, 134.0, 133.5,
133.4, 132.8, 132.5, 132.05, 130.9, 130.0, 129.2, 128.4, 128.2, 128.0, 127.96, 127.94, 127.83,
127.80, 127.5, 127.3, 126.9, 126.8, 126.6, 126.4, 126.3, 125.9, 125.8, 125.6, 124.5, 120.5, 119.2,
114.9, 113.9, 55.4, 55.3, 21.7, 21.6; IR (film): 3268, 3061, 1418, 1244, 1089 cmꢀ1; HRMS (EI): m/z
calcd for C26H23NO3S : 429.1399; found : 429.1399.
N-(2-(4-Methoxyphenyl)-2-(thiophen-3-yl)vinyl)-4-methylbenzenesulfonamide (3pa) : 46.2 mg
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(60%), Rf = 0.35 (EtOAc:hexane = 1:3); yellow oil; E/Z ratio 3:1; 1H NMR (400 MHz, CDCl3), data
for the major isomer; δ 7.70 (d, J = 8.3 Hz, 2H), 7.37ꢀ7.32 (m, 2H), 7.25 (t, J = 4.0 Hz, 1H), 7.08ꢀ
7.04 (m, 1H), 6.89ꢀ6.84 (m, 4H), 6.80 (t, J = 4.4 Hz, 1H), 6.69ꢀ6.66 (m, 1H), 6.18 (d, J = 11.5 Hz,
1H), 3.83 (s, 3H), 2.44 (s, 3H); data for the minor isomer; 7.74 (d, J = 8.3 Hz, 2H), 7.37ꢀ7.32 (m,
2H), 7.25 (t, J = 4.0 Hz, 2H), 7.08ꢀ7.04 (m, 2H), 6.89ꢀ6.84 (m, 1H), 6.77 (s, 1H), 6.69ꢀ6.66 (m, 2H),
6.42 (d, J = 11.5 Hz, 1H), 3.78 (s, 3H), 2.44 (s, 3H); 13C{1H} NMR (100 MHz, CDCl3) δ 159.4,
159.0, 144.0, 143.97, 141.3, 136.8, 136.7, 136.6, 131.8, 130.5, 130.0, 129.9, 128.4, 128.3, 127.9,
127.7, 127.1, 126.0, 124.9, 124.2, 121.8, 121.1, 120.8, 119.5, 114.8, 113.8, 55.4, 21.6; IR (film):
3269, 3065, 1718, 1636, 1509, 1338, 1169, 1089 cmꢀ1; HRMS (EI): m/z calcd for C20H19NO3S2 :
385.0806; found : 385.0804.
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N-(1-(4-Methoxyphenyl)-3,4-dihydronaphthalen-2-yl)-4-methylbenzenesulfonamide (3qa)
56.7 mg (70%), Rf = 0.3 (EtOAc:hexane = 1:4); pale yellow oil; 1H NMR (400 MHz, CDCl3)
:
δ
7.59
(app d, J = 8.2 Hz, 2H), 7.30 (d, J = 8.0 Hz, 2H), 7.11 (dd, J = 7.3, 0.9 Hz, 1H), 7.04 (td, J = 11.0,
1.3 Hz, 1H), 6.96 (td, J = 11.3, 1.3 Hz, 1h), 6.87 (app d, J = 8.6 Hz, 2H), 6.62 (app d, J = 8.6 Hz,
2H), 6.43 (dd, J = 7.6, 0.7 Hz, 1H), 6.26 (s, 1H), 3.85 (s, 3H), 2.85 (s, 3H); 13C{1H} NMR (100
MHz, CDCl3)
δ 159.3, 144.0, 136.1, 135.8, 133.8, 132.1, 131.2, 129.7, 127.3, 127.0, 126.7, 126.4,
126.3, 125.3, 124.8, 114.8, 55.3, 28.1, 24.5, 21.6; IR (film): 3319, 2936, 1608, 1335, 1164, 912 cmꢀ
1; HRMS (EI): m/z calcd for C24H23NO3S : 405.1399; found : 405.1396.
N-(2-(4-Ethoxyphenyl)-2-phenylvinyl)-4-methylbenzenesulfonamide (4ab) : 55.9 mg (71%), Rf
= 0.4 (EtOAc:hexane = 1:3); pale yellow oil; E/Z ratio 2.27:1; 1H NMR (400 MHz, CDCl3) data for
the major isomer; δ 7.72 (app d, J = 8.3 Hz, 2H), 7.34 (app d, J = 8.3 Hz, 2H), 7.35ꢀ7.30 (m, 1H),
7.25ꢀ7.18 (m, 2H), 7.12ꢀ7.08 (m, 2H), 6.89ꢀ6.79 (m, 4H), 6.76 (d, J = 11.5 Hz, 1H), 6.28 (d, J =
11.5 Hz, 1H), 4.04 (q, J = 6.9 Hz, 2H), 2.45 ( s, 3H), 1.44 (t, J = 6.9 Hz, 3H); data for the minor
isomer; 7.71 (app d, J = 8.3 Hz, 2H), 7.35ꢀ7.30 (m, 2H), 7.25ꢀ7.18 (m, 3H), 7.01 (app d, J = 8.8 Hz,
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2H), 6.89ꢀ6.79 (m, 2H), 6.77 (app d, J = 8.8 Hz, 2H), 6.68 (d, J = 11.5 Hz, 1H), 6.19 (d, J = 11.5 Hz,
1H), 3.99 (q, J = 6.8 Hz, 2H), 2.45 (s, 3H), 1.39 (t, J = 7.0 Hz, 3H); 13C{1H} NMR (100 MHz,
CDCl3) δ 158.7, 158.3, 144.0, 143.9, 139.7, 136.7, 136.67, 136.6, 131.8, 130.8, 129.94, 129.92,
129.5, 129.3, 128.4, 128.1, 127.7, 127.0, 126.83, 126.81, 126.6, 126.3, 126.0, 120.0, 118.7, 115.3,
114.3, 63.5, 63.4, 21.6, 14.85, 14.82; IR (film): 3269, 2980, 1509, 1335, 1164, 813, 669 cmꢀ1;
HRMS (EI): m/z calcd for C23H23NO3S : 393.1399; found : 393.1396.
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4-Methyl-N-(2-(4-phenoxyphenyl)-2-phenylvinyl)benzenesulfonamide (4ac) : 72.4 mg (82%), Rf
= 0.3 (EtOAc:hexane = 1:3); pale yellow solid; mp 148ꢀ153 oC; E/Z ratio 10:1; 1H NMR (400 MHz,
CDCl3) δ 7.72 (d, J = 8.3 Hz, 2.3H), 7.39ꢀ7.30 (m, 8H), 7.24ꢀ7.16 (m, 0.4H), 7.13ꢀ7.04 (m, 3.6H),
7.00ꢀ6.98 (m, 2H), 6.94ꢀ6.86 (m, 4.6H), 6.78 (d, J = 11.6 Hz, 0.14H), 6.74 (d, J = 11.6 Hz, 1H),
2.45 (s, 3H), 2.43 (s, 0.3H); 13C{1H} NMR (100 MHz, CDCl3) δ 157.5, 157.0, 156.6, 156.3, 144.1,
144.0, 139.0, 136.70, 136.68, 136.4, 134.5, 131.1, 130.7, 130.0, 129.9, 129.8, 129.7, 129.6, 129.4,
128.4, 128.3, 127.9, 127.2, 126.82, 126.80, 126.6, 125.7, 125.5, 124.0, 123.4, 120.3, 119.64, 119.60,
119.02, 119.00, 118.6, 21.7; IR (film): 3265, 3063, 1719, 1350, 1244, 1089 cmꢀ1; HRMS (EI): m/z
calcd for C27H23NO3S : 441.1399; found : 441.1397.
N-(2-(4-(4-Methoxyphenoxy)phenyl)-2-phenylvinyl)-4-methylbenzenesulfonamide (4ad) : 75.4
mg (80%), Rf = 0.3 (EtOAc:hexane = 1:3); yellow oil; E/Z ratio 1.1:1; 1H NMR (400 MHz, CDCl3),
data for the major isomer;
δ 7.73ꢀ7.70 (m, 3.6H), 7.36ꢀ7.33 (m, 7H), 7.25ꢀ7.21 (m, 2.8H), 7.12ꢀ7.10
(m, 4H), 6.97ꢀ6.87 (m, 9.1H), 6.86ꢀ6.80 (m, 4.5H), 6.77 (d, J = 11.6 Hz, 1H), 6.71 (d, J = 11.6 Hz,
1H), 6.30 (d, J = 11.6 Hz, 1H), 6.22 (d, J = 11.6 Hz, 1H), 3.83 (s, 2.8H), 3.80 (s, 3H), 2.46 (s, 2.8H),
2.44 (s, 3H); 13C{1H} NMR (100 MHz, CDCl3)
δ 158.7, 157.9, 156.3, 156.0, 149.8, 149.2, 144.1,
144.0, 139.5, 136.7, 136.6, 136.4, 133.7, 131.0, 130.0, 129.94, 129.90, 129.5, 129.4, 128.4, 128.2,
127.8, 127.1, 126.8, 126.7, 126.6, 125.8, 125.5, 121.4, 120.9, 120.2, 119.3, 117.8, 117.3, 115.0,
114.9, 55.7, 21.6; IR (film): 3268, 1687, 1649, 1498, 1336, 1231, 1163 cmꢀ1; HRMS (EI): m/z calcd
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for C28H25NO4S : 471.1504; found : 471.1500.
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mg (70%), Rf = 0.4 (EtOAc:hexane = 1:3); yellow oli; E/Z ratio 1.7:1; 1H NMR (400 MHz, CDCl3)
δ 7.72ꢀ7.68 (m, 3.4H), 7.33ꢀ7.29 (m, 3.5H), 7.23ꢀ7.20 (m, 2.8H), 7.19ꢀ7.16 (m, 1.4H), 7.13ꢀ7.10 (m,
1.3H), 7.09ꢀ7.07 (m, 2H), 6.90 (d, J = 11.6 Hz, 1H), 6.83 (d, J = 11.3 Hz, 0.62H), 6.78 (d, J = 2.5
Hz, 1H), 6.74 (s, 0.9H), 6.72ꢀ6.69 (m, 1.4H), 6.65ꢀ6.62 (m, 1.7H), 6.21 (d, J = 11.3 Hz, 0.62H),
6.00 (d, J = 11.6 Hz, 1H), 3.82 (s, 3H), 3.52 (s, 1.87H), 2.43 (s, 3H), 2.42 (s, 1.76H), 2.37 (s,
1.89H); 13C{1H} NMR (100 MHz, CDCl3) δ 159.6, 156.7, 144.0, 143.7, 140.1, 139.5, 138.9, 138.5,
137.2, 136.9, 131.4, 131.1, 129.9, 129.7, 128.5, 128.3, 126.87, 126.85, 126.8, 126.7, 126.6, 126.0,
125.4, 124.8, 122.1, 121.9, 121.4, 120.9, 120.5, 116.4, 112.7, 112.1, 55.5, 55.2, 21.66, 21.61, 21.6,
19.4; IR (film): 3258, 2923, 1348, 1167, 813, 667 cmꢀ1; HRMS (EI): m/z calcd for C23H23NO3S :
393.1399; found : 393.1400.
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N-(2-(3,4-Dimethoxyphenyl)-2-phenylvinyl)-4-methylbenzenesulfonamide (4af) : 59.8 mg
(73%), Rf = 0.2 (EtOAc:hexane = 1:3); white solid; mp 173.8ꢀ176.3 °C; E/Z ratio 3.8:1; 1H NMR
(400 MHz, CDCl3) data for the major isomer; δ 7.73 (app d, J = 8.3 Hz, 2H), 7.33 (app d, J = 7.8
Hz, 2H), 7.36ꢀ7.32 (m, 1H), 7.28ꢀ7.19 (m, 2H), 7.14ꢀ7.11 (m, 2H), 6.84 (d, J = 8.2 Hz, 1H), 6.80 (d,
J = 11.5 Hz, 1H), 6.50 (dd, J = 8.1, 1.9 Hz, 1H), 6.42 (d, J = 1.9 Hz, 1H), 6.34 (d, J = 11.5 Hz, 1H),
3.91 (s, 3H), 3.69 (s, 3H), 2.44 (s, 3H); data for the minor isomer; 7.72 (app d, J = 8.3 Hz, 2H),
7.36ꢀ7.33 (m, 2H), 7.28ꢀ7.19 (m, 3H), 6.89ꢀ6.87 (m, 2H), 6.74 (d, J = 8.4 Hz, 1H), 6.71 (d, J = 11.5
Hz, 1H), 6.65 (d, J = 2.1 Hz, 1H), 6.59 (dd, J = 8.3, 2.1 Hz, 1H), 6.21 (d, J = 11.5 Hz, 1H), 3.85 (s,
3H), 3.80 (s, 3H), 2.46 (s, 3H) ; 13C{1H} NMR (100 MHz, CDCl3) δ 149.7, 148.8, 148.5, 144.0,
143.9, 139.4, 136.9, 136.6, 136.5, 132.4, 129.9, 129.5, 129.3, 128.6, 128.4, 128.2, 127.1, 126.8,
126.7, 126.4, 125.8, 121.9, 120.1, 119.5, 119.0, 112.4, 111.7, 110.9, 109.7, 56.0, 55.9, 55.8, 21.65,
21.61; IR (film): 3213, 2932, 1513, 1160, 768 cmꢀ1; HRMS (EI): m/z calcd for C23H23NO4S :
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409.1348; found : 409.1349.
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N-(2-(2,4-Dimethoxyphenyl)-2-phenylvinyl)-4-methylbenzenesulfonamide (4ag) : 63.1 mg
(77%), Rf = 0.2 (EtOAc:hexane = 1:3); white solid; mp 82.3ꢀ85.3 oC; 1H NMR (400 MHz, CDCl3) δ
7.73ꢀ7.70 (m, 2H), 7.31 (d, J = 8.0 Hz, 2H), 7.25ꢀ7.20 (m, 2H), 7.19ꢀ7.15 (m, 1H), 7.13ꢀ7.10 (m,
2H), 6.84 (d, J = 11.4 Hz, 1H), 6.69 (d, J = 8.3 Hz, 1H), 6.49 (d, J = 2.3 Hz, 1H), 6.46 (dd, J = 8.3,
2.4 Hz, 1H), 6.20 (d, J = 11.3 Hz, 1H), 3.84 (s, 3H), 3.51 (s, 3H), 2.43 (s, 3H); 13C{1H} NMR (100
MHz, CDCl3) δ 161.1, 157.9, 143.7, 139.7, 137.2, 132.2, 129.8, 128.3, 126.8, 126.7, 126.0, 121.7,
120.9, 116.8, 105.5, 99.3, 55.6, 55.5, 21.6; IR (film): 3248, 2940, 1600, 1317, 1161, 1029, 814 cmꢀ
1; HRMS (EI): m/z calcd for C23H23NO4S : 409.1348; found : 409.1345.
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mg (65%), Rf = 0.3 (EtOAc:hexane = 1:3); white solid; mp 168.3ꢀ171 C; E/Z ratio 7.7:1; 1H NMR
(400 MHz, CDCl3) data for the major isomer; δ 7.72 (app d, J = 8.2 Hz, 2H), 7.34 (app d J = 8.0
Hz, 2H), 7.27ꢀ7.18 (m, 3H) 7.12 (app d, J = 8.2 Hz, 2H), 6.74 (d, J = 11.5 Hz, 1H), 6.72 (d, J = 8.1
Hz, 1H), 6.68 (s, 1H), 6.59 (dd, J = 8.1, 1.6 Hz, 1H), 6.29 (d, J = 11.5 Hz, 1H), 4.59 (t, 8.7 Hz, 2H),
3.14 (t, J = Hz, 2H), 2.45 (s, 3H); data for the minor isomer; 7.71 (app d, J = 8.1 Hz, 2H), 7.35ꢀ7.31
(m, 3H), 7.27ꢀ7.18 (m, 2H), 6.96 (s, 1H), 6.88ꢀ6.86 (m, 2H), 6.83 (dd, J = 8.2, 1.8 Hz, 1H), 6.67 (d,
J = 9.7 Hz, 1H), 6.66 (d, J = 11.7 Hz, 1H), 6.18 (d, J = 11.6 Hz, 1H), 4.54 (t, J = 8.7 Hz, 2H), 3.14
(t, J = 8.7 Hz, 2H), 2.45 Hz (s, 3H); 13C{1H} NMR (100 MHz, CDCl3)
δ 160.0, 159.6, 144.0, 143.9,
139.8, 136.8, 136.7, 136.6, 132.2, 129.9, 129.5, 129.4, 129.3, 128.3, 128.1, 127.3, 127.0, 126.8,
126.7, 126.6, 126.5, 126.2, 123.2, 119.9, 118.5, 110.0, 109.0, 71.4, 29.6, 21.6; IR (film): 3252, 2919,
1492, 1348, 1167, 669 cmꢀ1; HRMS (EI): m/z calcd for C23H21NO3S : 391.1242 ; found : 391.1243.
N-(2-(Benzo[d][1,3]dioxol-5-yl)-2-phenylvinyl)-4-methylbenzenesulfonamide (4ai) : 55.1 mg
(70%), Rf = 0.3 (EtOAc:hexane = 1:3); white solid; mp 68.9ꢀ72.5 oC; E/Z ratio 1.42:1; 1H NMR 400
MHz, CDCl3) data for the major isomer; δ 7.72 (app d, J = 8.3 Hz, 2H), 7.34 (app d, J = 7.2 Hz,
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2H), 7.35ꢀ7.31 (m, 1H), 7.27ꢀ7.21 (, 2H), 7.11 (app d, J = 8.3 Hz, 2H), 6.78 (d, J = 7.9 Hz, 1H),
6.75 (d, J = 11.6 Hz, 1H), 6.38 (dd, J = 7.9, 1.6 Hz, 1H), 6.33 (d, J = 1.6 Hz, 1H), 6.32 (d, J = 11.6
Hz, 1H), 5.99 (s, 2H), 2.45 (s, 3H); data for the minor isomer; 7.71 (app d, J = 8.2 Hz, 2H), 7.35ꢀ
7.31 (m, 2H), 7.27ꢀ7.21 (m, 3H), 6.89ꢀ6.87 (m, 2H), 6.68 (d, J = 8.0 Hz, 1H), 6.66 (d, J = 11.4 Hz,
1H), 6.59 (d, J = 1.7 Hz, 1H), 6.54 (dd, J = 8.0, 1.8 Hz, 1H), 6.20 (d, J = 11.5 Hz, 1H), 5.92 (s, 2H),
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2.46 (s, 3H); 13C{1H} NMR (100 MHz, CDCl3)
δ 148.5, 147.8, 147.5, 146.9, 144.0, 144.0, 139.4,
136.66, 136.64, 136.4, 133.8, 130.0, 129.9, 129.5, 129.4, 128.4, 128.2, 127.1, 126.8, 126.7, 126.2,
125.8, 122.9, 120.5, 120.3, 119.2, 109.9, 109.1, 108.1, 107.0, 101.3, 101.1, 21.6; IR (film): 3280,
3060, 2897, 1487, 1352, 1166, 812 cmꢀ1; HRMS (EI): m/z calcd for C22H19NO4S : 393.1035 ;
found : 393.1032.
N-(2-(4-Methoxynaphthalen-1-yl)-2-phenylvinyl)-4-methylbenzenesulfonamide (4aj)7 : 68.7
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mg (80%), Rf = 0.3 (EtOAc:hexane = 1:3); white solid; mp 170ꢀ173.3 C; H NMR (400 MHz,
CDCl3) δ 8.29 (d, J = 8.4 Hz, 1H), 7.60 (d, J = 8.3 Hz, 2H), 7.43 (ddd, J = 8.2, 6.7, 1.2 Hz, 1H),
7.28ꢀ7.25 (m, 3H), 7.21ꢀ7.15 (m, 3H), 7.14ꢀ7.11 (m, 3H), 7.09 (d, J = 11.6 Hz, 1h), 7.00 (d, J = 7.8
Hz, 1H), 6.80 (d, J = 7.9 Hz, 1H), 5.98 (d, J = 11.6 Hz, 1H), 4.04 (s, 3H), 2.45 (s, 3H); 13C{1H}
NMR (100 MHz, CDCl3)
δ 155.9, 143.9, 139.3, 136.8, 132.2, 129.8, 128.5, 128.2, 127.1, 126.9,
126.8, 126.2, 125.6, 125.5, 124.8, 124.7, 123.7, 122.5, 121.6, 103.8, 55.6, 21.6; IR (film): 3266,
3062, 1585, 1348, 1162, 1089, 764 cmꢀ1; HRMS (EI): m/z calcd for C26H23NO3S : 429.1399 ;
found : 429.1398.
4-Methyl-N-(2-phenyl-2-(2,4,5-trimethoxyphenyl)vinyl)benzenesulfonamide (4ak) : 62.4 mg
(71%), Rf = 0.2 (EtOAc:hexane = 1:3); pale yellow oil; 1H NMR (400 MHz, CDCl3) δ 7.73 (app d, J
= 8.3 Hz, 2H), 7.30 (d, J = 8.0 Hz, 2H), 7.27ꢀ7.23 (m, 2H), 7.21ꢀ7.18 (m, 1H), 7.17ꢀ7.14 (m, 2H),
6.85 (d, J = 11.2 Hz, 1H), 6.56 (s, 1H), 6.35 (d, J = 11.2 Hz, 1H), 6.29 (s, 1H), 3.93 (s, 3H), 3.63 (s,
3H), 3.49 (s, 3H), 2.41 (s, 3H); 13C{1H} NMR (100 MHz, CDCl3)
δ 151.1, 149.8, 143.8, 143.6,
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139.6, 137.3, 129.7, 128.4, 126.8, 126.2, 121.4, 121.1, 115.8, 114.2, 98.8, 57.0, 56.1, 21.5; IR
(film): 3259, 2935, 1511, 1158, 811, 668 cmꢀ1; HRMS (EI): m/z calcd for C24H25NO5S : 439.1453 ;
found : 439.1451.
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(53%), Rf = 0.15 (EtOAc:hexane = 1:3); white solid; mp 165ꢀ168 oC; 1H NMR (400 MHz, CDCl3) δ
7.71 (app d, J = 8.3 Hz, 2H), 7.28 (d, J = 8.3 Hz, 2H), 7.22ꢀ7.18 (m, 2H), 7.15ꢀ7.11 (m, 3H), 6.92 (d,
J = 11.4 Hz, 1H), 6.13 (s, 2H), 6.10 (d, J = 10.4 Hz, 1H), 3.85 (s, 3H), 3.45 (s, 6H), 2.40 (s, 3H);
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13C{1H} NMR (100 MHz, CDCl3)
δ 161.8, 158.8, 143.4, 139.2, 137.7, 129.6, 128.2, 126.8, 126.3,
125.1, 121.5, 117.1, 104.6, 91.0, 55.6, 55.4, 21.5; IR (film): 3260, 2939, 1587, 1328, 1161, 813 cmꢀ
1; HRMS (EI): m/z calcd for C24H25NO5S : 439.1453 ; found : 439.1454.
N-(2-(4-Methoxy-2-(pent-2-yn-1-yloxy)phenyl)-2-phenylvinyl)-4-methylbenzenesulfonamide
(4am) : 81.2 mg (88%), Rf = 0.35 (EtOAc:hexane = 1:3); brown oil; E/Z ratio 1.5:1; 1H NMR (400
MHz, CDCl3), data for the major isomer; δ 7.71 (dt, J = 8.7, 1.9 Hz, 2H), 7.30 (d, J = 8.4 Hz, 2H),
7.24ꢀ7.10 (m, 4H), 6.84 (d, J = 11.4 Hz, 1H), 6.70ꢀ6.67 (m, 1H), 6.57 (d, J = 2.4 Hz, 1H), 6.53ꢀ6.49
(m, 1H), 6.24 (d, J = 11.4 Hz, 1H), 4.68 (t, J = 2.1 Hz, 2H), 3.49 (s, 3H), 2.42 (s, 3H), 2.25 (qt, J =
12.5, 2.1 Hz, 2H), 1.16 (t, J = 7.5 Hz, 3H); data for the minor isomer; 7.75 (dt, J = 8.7, 1.9 Hz, 2H),
7.30 (d, J = 8.4 Hz, 2H), 7.24ꢀ7.10 (m, 4H), 6.80 (d, J = 11.4 Hz, 1H), 6.71 (d, J = 8.4 Hz, 1H),
6.69ꢀ6.67 (m, 1H), 6.52ꢀ6.49 (m, 1H), 6.34 (d, J = 11.3 Hz, 1H), 4.34 (t, J = 2.1 Hz, 2H), 3.83 (s,
3H), 2.42 (s, 3H), 2.18 (qt, J = 12.5, 2.1 Hz, 3H); 13C{1H} NMR (100 MHz, CDCl3)
δ 160.7, 159.4,
157.9, 155.8, 143.7, 143.6, 140.0, 139.7, 137.3, 137.2, 132.3, 132.1, 129.8, 129.7, 128.3, 128.2,
126.9, 126.8, 126.7, 126.6, 126.3, 126.0, 121.6, 121.2, 121.03, 121.00, 117.7, 117.3, 106.9, 106.5,
101.2, 100.2, 90.3, 90.0, 77.3, 74.0, 73.9, 56.68, 56.65, 55.6, 55.5, 21.6, 13.7, 13.6, 12.6, 12.5; IR
(film): 3276, 3061, 3029, 2976, 1606, 1348, 1164, 1090 cmꢀ1; HRMS (EI): m/z calcd for
C27H27NO4S : 461.1661 ; found : 461.1662.
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N-(2-(4-(4-Bromobutoxy)phenyl)-2-phenylvinyl)-4-methylbenzenesulfonamide (4an) : 70.7 mg
(70%), Rf = 0.35 (EtOAc:hexane = 1:3); yellow oil; E/Z ratio 1.36:1; 1H NMR (400 MHz, CDCl3),
data for the major isomer; δ 7.72 (d, J = 8.3 Hz, 2H), 7.34ꢀ7.30 (m, 2H), 7.26ꢀ.7.18 (m, 2H), 7.11ꢀ
7.08 (m, 2H), 6.89ꢀ6.77 (m, 4H), 6.75 (d, J = 3.2 Hz, 1H), 6.30 (d, J = 11.6 Hz, 1H), 4.00 (t, J = 6.0
Hz, 2H), 3.51 (t, J = 6.6 Hz, 2H), 2.44 (s, 3H), 2.12ꢀ1.88 (m, 4H); data for the minor isomer; 7.71 (d,
J = 8.3 Hz, 2H), 7.34ꢀ7.30 (m, 3H), 7.26ꢀ7.18 (m, 2H), 7.01 (dt, J = 9.8, 2.5 Hz, 2H), 6.89ꢀ6.77 (m,
4H), 6.69 (d, J = 11.5 Hz, 1H), 6.22 (d, J = 11.6 Hz, 1H), 3.95 (t, J = 6.0 Hz, 2H), 3.47 (t, J = 6.6
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Hz, 2H), 2.44 (s, 3H), 2.12ꢀ1.88 (m, 4H); 13C{1H} NMR (100 MHz, CDCl3)
δ 158.7, 158.2, 144.0,
143.9, 139.7, 136.7, 136.6, 136.5, 132.1, 130.9, 130.0, 129.9, 129.6, 129.4, 128.4, 128.1, 127.8,
127.1, 126.8, 126.7, 126.6, 126.2, 125.9, 120.1, 118.8, 115.3, 114.3, 66.9, 66.8, 33.5, 29.4, 27.9,
21.7; IR (film): 3271, 3059, 2950, 1722, 1350, 1163, 1083, 543 cmꢀ1; HRMS (EI): m/z calcd for
C25H26BrNO3S : 499.0817 ; found : 499.0819.
N-(2-(2-Bromophenyl)-2-(4-phenoxyphenyl)vinyl)-4-methylbenzenesulfonamide (4lc) : 69.6 mg
(65%), Rf = 0.3 (EtOAc:hexane = 1:3); ivory solid; mp 167ꢀ170 oC; 1H NMR (400 MHz, CDCl3); δ
7.72 (d, J = 8.3 Hz, 2H), 7.62 (dd, J = 8.0, 1.2 Hz, 1H), 7.34ꢀ7.29 (m, 5H), 7.25ꢀ7.21 (m, 1H), 7.11ꢀ
7.07 (m, 1H), 7.03 (dt, J = 9.6, 2.5 Hz, 2H), 7.00ꢀ6.97 (m, 2H), 6.93 (dd, J = 7.5, 1.7 Hz, 1H), 6.89ꢀ
6.83 (m, 3H), 6.01 (d, J = 11.6 Hz, 1H), 2.42 (s, 3H); 13C{1H} NMR (100 MHz, CDCl3)
δ 156.9,
156.5, 144.1, 136.9, 136.6, 133.8, 132.8, 131.9, 130.2, 129.9, 129.8, 128.4, 127.0, 126.9, 124.5,
123.7, 123.5, 120.6, 119.0, 118.7, 21.6; IR (film): 3222, 1705, 1659, 1471, 1320, 1204, 540 cmꢀ1;
HRMS (EI): m/z calcd for C27H22BrNO3S : 519.0504 ; found : 519.0502.
N-(2-(2-Bromophenyl)-2-(2,4-dimethoxyphenyl)vinyl)-4-methylbenzenesulfonamide (4lg)
:
o
87.9 mg (90%), Rf = 0.3 (EtOAc:hexane = 1:3); brown soild; mp 34ꢀ40 C; E/Z ratio 3:1; 1H NMR
(400 MHz, CDCl3), data for the major isomer; δ 7.75 (d, J = 8.2 Hz, 2H), 7.48 (d, J = 7.8 Hz, 1H),
7.31 (d, J = 8.2 Hz, 2H), 7.27ꢀ7.24 (m, 2H), 7.12ꢀ7.07 (m, 1H), 6.80 (d, J = 11.0 Hz, 1H), 6.68 (d, J
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= 8.5 Hz, 1H), 6.50ꢀ6.46 (m, 2H), 6.38 (dd, J = 8.5, 2.4 Hz, 1H), 3.77 (s, 3H), 3.63 (s, 3H), 2.43 (s,
3H); data for the minor isomer; 7.73 (d, J = 8.7 Hz, 2H), 7.57 (dd, J = 8.0, 1.0 Hz, 1H), 7.31 (d, J =
8.2 Hz, 2H), 7.27ꢀ7.24 (m, 1H), 7.21ꢀ7.14 (m, 2H), 7.11ꢀ7.01 (m, 1H), 6.96 (dd, J = 7.5, 1.7 Hz,
1H), 6.68 (d, J = 8.5 Hz, 1H), 6.44 (d, J = 2.4 Hz, 1H), 6.33 (dd, J = 8.6, 2.4 Hz, 1H), 5.95 (d, J =
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11.9 Hz, 1H), 3.75 (s, 3H), 3.74 (s, 3H), 2.42 (s, 3H); 13C{1H} NMR (100 MHz, CDCl3)
δ 160.7,
159.7, 15.8, 157.1, 143.77, 143.66, 141.8, 137.9, 137.5, 137.1, 133.5, 133.2, 132.08, 132.06, 131.6,
130.5, 129.7, 129.5, 128.5, 128.1, 127.2, 127.0, 126.8, 124.4, 124.2, 124.1, 123.3, 120.7, 120.4,
119.7, 118.0, 105.5, 104.2, 99.4, 99.2, 55.9, 55.5, 55.4, 55.3, 21.6; IR (film): 3279, 3062, 2937,
1607, 1347, 1164, 1090, 544 cmꢀ1; HRMS (EI): m/z calcd for C23H22BrNO4S : 487.0453 ; found :
487.0456.
N-(2-(2-Bromophenyl)-2-(2,3-dihydrobenzofuran-5-yl)vinyl)-4-methylbenzenesulfonamide
(4lh) : 53.6 mg (57%), Rf = 0.3 (EtOAc:hexane = 1:3); ivory solid; mp 51ꢀ53 oC; E/Z ratio 1.5:1; 1H
NMR (400 MHz, CDCl3), data for the major isomer; 7.71 (d, J = 8.4 Hz, 2H), 7.61 (dd, J =8.0, 1.2
Hz, 1H), 7.31ꢀ7.29 (m, 2H), 6.96 (d, J = 1.4 Hz, 1H), 6.88 (dd, J = 7.6, 1.9 Hz, 1H), 6.79ꢀ6.76 (m,
2H), 6.73ꢀ6.64 (m, 3H), 5.97 (d, J = 11.6 Hz, 1H), 4.56ꢀ4.51 (m, 2H), 3.12 (q, J = 8.6 Hz, 2H), 2.43
(s, 3H); data for the minor isomer; 7.76 (d, J = 8.3 Hz, 2H), 7.51 (dd, J = 7.9, 1.1 Hz, 1H), 7.35ꢀ
7.34 (m, 2H), 7.31ꢀ7.29 (m, 1H), 7.28ꢀ7.26 (m, 1H), 7.24ꢀ7.22 (m, 2H), 7.17ꢀ7.10 (m, 2H), 6.80ꢀ
6.76 (m, 1H), 6.42 (d, J = 11.6 Hz, 1H), 4.56ꢀ4.51 (m, 2H), 3.12 (q, J = 8.6 Hz, 2H), 2.45 (s, 3H);
13C{1H} NMR (100 MHz, CDCl3)
δ 159.7, 159.5, 144.1, 144.0, 141.2, 137.1, 136.9, 136.86, 133.7,
133.2, 132.1, 131.9, 130.4, 130.0, 129.93, 129.90, 128.9, 128.7, 128.5, 128.3, 128.0, 127.6, 127.3,
127.0, 125.9, 125.4, 124.6, 124.5, 124.4, 124.2, 122.9, 122.2, 119.5, 109.7, 109.2, 77.3, 71.5, 29.64,
29.60, 21.66, 21.63; IR (film): 3267, 1641, 1348, 1166, 1147, 1090, 667 cmꢀ1; HRMS (EI): m/z
calcd for C23H20BrNO3S : 469.0347 ; found : 469.0346.
Synthetic procedure of indene derivatives via intramolecular arylation : Solvent was added to a
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