Platinum(II)-catalyzed asymmetric ring-opening addition of arylboronic acids to oxabenzonorbornadienes

Article abstract of DOI:10.1021/jo402386k

A new platinum(II)-catalyzed asymmetric ring-opening addition of arylboronic acids to oxabenzonorbornadienes was developed, which afforded the corresponding cis-2-aryl-1,2-dihydronaphthalen-1-ol products in high yields (up to 97%) with moderate to good enantioselectivities (up to 89% ee) under very mild conditions. The effects of various ligands, catalyst loading, bases, solvents, and temperatures on the yield and enantioselectivity of the reaction were also investigated. The cis configuration of product 2m was confirmed by X-ray diffraction analysis. A potential mechanism for the present catalytic reaction is proposed.

Full text of DOI:10.1021/jo402386k

Article
pubs.acs.org/joc
Platinum(II)-Catalyzed Asymmetric Ring-Opening Addition of
Arylboronic Acids to Oxabenzonorbornadienes
Xuejing Pan, Guobao Huang, Yuhua Long, Xiongjun Zuo, Xuan Xu, Fenglong Gu, and Dingqiao Yang*
Key Laboratory of Theoretical Chemistry of Environment, Ministry of Education, School of Chemistry and Environment, South
China Normal University, Guangzhou 510006, People’s Republic of China
S
* Supporting Information
ABSTRACT: A new platinum(II)-catalyzed asymmetric ring-opening addition of arylboronic acids to oxabenzonorbornadienes
was developed, which afforded the corresponding cis-2-aryl-1,2-dihydronaphthalen-1-ol products in high yields (up to 97%) with
moderate to good enantioselectivities (up to 89% ee) under very mild conditions. The effects of various ligands, catalyst loading,
bases, solvents, and temperatures on the yield and enantioselectivity of the reaction were also investigated. The cis configuration
of product 2m was confirmed by X-ray diffraction analysis. A potential mechanism for the present catalytic reaction is proposed.
generated via the enantioselective cleavage of a carbon−
heteroatom bond followed by an SN2′ nucleophilic displace-
ment. Our continuous interest in developing ARO of oxa- and
azabicyclic alkenes prompted us to explore other transition-
metal catalysts to expand the scope of the reactions. In this
article, we report a novel ARO addition of arylboronic acids to
oxabenzonorbornadienes in the presence of platinum complex
and KF solution (5 M in H2O) to afford the corresponding
ring-opening products of cis-2-aryl-1,2-dihydronaphthalen-1-ols
in high yields (up to 97%) with moderate to good
enantioselectivities (up to 89% ee). The 1,2-cis products,
potential valuable scaffolds for the synthesis of optically active
compounds, were generated by transmetalation−enantioselec-
tive addition to the CC bond over the enantioselective C−O
bond cleavage. Compared to the results with Rh or Pd, the
ring-opening addition reactions catalyzed by Pt showed better
reactivity and higher enantioselectivity.
INTRODUCTION
■
The transition-metal-catalyzed asymmetric ring-opening
(ARO) reactions of oxa- and azabicyclic alkenes undoubtedly
provide an efficient synthetic tool for the selective formation of
carbon−carbon and carbon−heteroatom bonds.1 This process
is especially valuable as multiple stereocenters can be
established rapidly and efficiently in a single step. Many
metal catalysts, such as Fe,2 Ni,3 Cu,4 Ru,5 Rh,6 Pd,7 and so
forth, have been investigated for ring-opening reactions with
heteroatom nucleophiles8 and carbanion nucleophiles.9
Organoboronic acids are ideal carbanion nucleophiles
because they are air- and moisture-tolerant.10 Rhodium- and
palladium-catalyzed ARO of oxa- and azabenzonorbornadienes
with arylboronic acids have been reported by Lautens et al.,11
Hou et al.,12 and Murakami et al.,13 and the cis-2-aryl-1,2-
dihydronaphthalen-1-ol products were produced in excellent
yields (up to 99%) with good enantioselectivities (up to 83%
ee). To the best of our knowledge, similar ARO reactions of
oxa- and azabicyclic alkenes with arylboronic acids in the
presence of other transition-metal catalysts remain unknown,
presenting a challenge to chemists.
RESULTS AND DISCUSSION
■
Substrates 1a−d were readily prepared by Diels−Alder
reactions according to literature procedures.17 We began our
studies by searching for the optimal platinum catalyst system. In
our initial experiments, oxabenzonorbornadiene 1a was treated
with phenylboronic acid in the presence of Pt(COD)Cl2 and
P,P or N,P ligand (Table 1). To explore the ring-opening
Our group has been interested in the ARO of oxa- and
azabenzonorbornadienes with various nucleophiles for some
time. In our previous work, we successfully demonstrated the
iridium-catalyzed ARO of oxa- and azabenzonorbornadienes
with various nucleophiles, including amines,14 phenols,15 and
alcohols,16 to afford the ring-opening products in high yields
with excellent enantioselectivities. The 1,2-trans products were
Received: October 25, 2013
© XXXX American Chemical Society
A
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a
Table 1. Effects of Chiral Ligand and Catalyst Loading
b
entry
Pt(COD)Cl2 (mol %)
ligand (mol %)
DPPP (2.5)
time (h)
yield (%)
ee (%)
1
2
2.5
2.5
2.5
2.5
2.5
2.5
2.5
1.5
3.0
4.0
24
22
22
48
96
24
20
56
17
17
80
87
86
77
31
89
90
67
85
80
0
(S)-BINAP (2.5)
80
64
75
20
77
82
78
78
75
3
(S)-p-Tol-BINAP (2.5)
(S)-(−)-XylBINAP (2.5)
(S)-PipPhos (2.5)
4
5
6
(S)-(−)-SEGPHOS (2.5)
(S)-(−)-DM-SEGPHOS (2.5)
(S)-(−)-DM-SEGPHOS (1.5)
(S)-(−)-DM-SEGPHOS (3.0)
(S)-(−)-DM-SEGPHOS (4.0)
7
8
9
10
a
The reaction was carried out with 1a (0.2 mmol), 3.0 equiv of phenylboronic acid (0.6 mmol), and 0.5 equiv of KF (5 M in H2O) in CH2Cl2 (2.0
b
mL) at 25 °C in the presence of Pt(COD)Cl2 and ligand. Determined by HPLC with a Chiralcel OD-H column.
a
Table 2. Combined Effects of Solvent, Base, and Temperature
b
c
entry
solvent
base
KF
temperature (°C)
time (h)
yield (%)
ee (%)
1
MeOH
iPrOH
THF
25
70
70
80
25
25
25
25
25
25
25
25
25
25
25
0
20
48
48
30
15
48
20
48
72
72
72
38
44
38
48
48
10
28
21
46
38
61
89
90
n.r.
65
21
16
85
60
75
56
51
55
96
84
79
55
86
78
82
2
KF
KF
KF
KF
KF
KF
3
4
toluene
DCE
5
6
CHCl3
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
7
8
9
KCl
69
66
71
75
87
81
85
84
76
10
11
12
13
14
15
16
17
KBr
KI
CsF
Cs2CO3
K3PO4
K2CO3
KF
KF
50
a
The reaction was carried out with 1a (0.2 mmol), 3.0 equiv of phenylboronic acid (0.6 mmol), and 0.5 equiv of base (5 M in H2O) in the solvent
b
(2.0 mL) of choice at the corresponding temperature in the presence of Pt(COD)Cl2 (2.5 mol %) and (S)-(−)-DM-SEGPHOS (2.5 mol %). Oil
bath temperature. Determined by HPLC with a Chiralcel OD-H column.
c
reaction, an achiral bisphosphine ligand DPPP was first chosen
to validate the catalytic activity of platinum complex in ARO of
1a with phenylboronic acid. Ring-opening product 2a was
obtained in an encouraging yield of 80% after 24 h (Table 1,
entry 1). Inspired by this result, we then attempted several
chiral ligands, including (S)-BINAP, (S)-p-Tol-BINAP, (S)-
B
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(−)-XylBINAP, (S)-PipPhos, (S)-(−)-SEGPHOS, and (S)-
(−)-DM-SEGPHOS, to optimize the reaction. Among the
ligands screened, (S)-(−)-DM-SEGPHOS was the most
effective and afforded 2a in 90% yield with 82% ee (Table 1,
entry 7). We next investigated the effect of catalyst loading on
the reaction. The results indicated that 2.5 mol % of
Pt(COD)Cl2 with 2.5 mol % of (S)-(−)-DM-SEGPHOS
would be a more suitable catalyst loading in terms of the
yield and enantioselectivity, whereas increasing or decreasing
the amount of catalyst loading improved neither the yield nor
ee value of 2a (Table 1, entries 8−10). Therefore, we decided
to choose 2.5 mol % of Pt(COD)Cl2/(S)-(−)-DM-SEGPHOS
as the best catalyst system to optimize the reaction further.
With the optimal chiral ligand and catalyst loading in hand,
we next screened the effects of different parameters, including
solvents, bases, and temperatures, on the reactivity and
enantioselectivity for the reaction (Table 2). Some common
solvents were initially tested (Table 2, entries 1−7). It was
observed that the reaction in protic solvents MeOH and iPrOH
gave excellent enantioselectivities (up to 96% ee) but poor
conversion (Table 2, entries 1 and 2). When the reaction was
carried out in THF, expected product 2a was afforded in only
46% yield with 79% ee (Table 2, entry 3), whereas the
employment of toluene gave a worse result (38% yield, 55% ee)
(Table 2, entry 4). Moderate to good yields and enantiose-
lectivities were obtained when DCE, CHCl3, and CH2Cl2 were
respectively employed as the solvents (Table 2, entries 5−7).
The study on solvent effect indicated that CH2Cl2 showed the
best combination of reactivity and enantioselectivity among all
solvents tested (90% yield, 82% ee). With CH2Cl2 as the
solvent, the reaction also required the addition of an inorganic
base and water to achieve good activity. It was observed that no
reaction occurred at all in the absence of a base (Table 2, entry
8). The impact of the base was further investigated to improve
the efficiency of the reaction (Table 2, entries 7, 9−15). When
the base was changed from KF to KCl, KBr, and KI, poor yields
and ee values of 2a were obtained (Table 2, entries 9−11).
Control experiments also revealed that strong bases, such as
KF, CsF, Cs2CO3, K3PO4, and K2CO3, could make the reaction
proceed smoothly, but they gave either unsatisfactory yields
(Table 2, entries 13−15) or undesirable ee values (Table 2,
entry 12) with the exception of KF, which exhibited positive
influence on the yield and enantioselectivity of 2a (Table 2,
entry 7). Temperature also play a crucial role in the ring-
opening reaction. By examining the effect of temperature, we
observed that the best result was obtained at 25 °C (90% yield,
82% ee) (Table 2, entry 7). When the reaction was carried out
at 0 °C, ring-opening product 2a was formed in 51% yield with
84% ee (Table 2, entry 16). Unexpectedly, the reaction at 50
°C required only 10 h to achieve complete conversion and
afforded 2a in 55% yield with 76% ee (Table 2, entry 17).
Therefore, the optimal reaction conditions were identified as
follows: 2.5 mol % of Pt(COD)Cl2/(S)-(−)-DM-SEGPHOS,
3.0 equiv of arylboronic acid, and 0.5 equiv of KF (5 M in
H2O) in CH2Cl2 at 25 °C.
Table 3. Platinum(II)-Catalyzed ARO Addition of Various
Arylboronic Acids to Oxabenzonorbornadiene 1a
a
b
entry
Ar
product time (h) yield (%) ee (%)
1
phenyl
2a
2b
2c
2d
2e
2f
20
72
44
20
44
42
21
62
19
19
90
46
42
39
42
62
48
42
96
96
90
78
79
86
90
48
84
trace
84
90
20
61
70
51
61
62
76
54
22
n.r.
82
68
46
68
44
49
75
2
4-bromophenyl
3-bromophenyl
4-chlorophenyl
3-chlorophenyl
2-chlorophenyl
4-fluorophenyl
4-acetylphenyl
4-methylphenyl
3-methylphenyl
2-methylphenyl
4-ethylphenyl
4-tert-butylphenyl
4-methoxyphenyl
3-methoxyphenyl
4-ethoxyphenyl
3,5-dimethylphenyl
2-naphthyl
3
4
5
6
7
2g
2h
2i
8
9
82
80
11
85
82
87
81
89
81
77
75
10
11
12
13
14
15
16
17
18
19
20
2j
2k
2l
2m
2n
2o
2p
2q
2r
2s
2t
3-thienyl
4-pyridinyl
a
The reaction was carried out with 1a (0.2 mmol), 3.0 equiv of
arylboronic acid (0.6 mmol), and 0.5 equiv of KF (5 M in H2O) in
CH2Cl2 (2.0 mL) at 25 °C in the presence of Pt(COD)Cl2 (2.5 mol
b
%) and (S)-(−)-DM-SEGPHOS (2.5 mol %). Determined by HPLC
with a Chiralcel OD-H column.
electron-donating systems were less reactive and more selective
(Table 3, entries 9−17). The ring-opening of 1a with para-
substituted phenylboronic acids offerd better enantioselectiv-
ities than those with meta- and ortho-substituted phenylboronic
acids (Table 3, entries 2−6, 9−11 and 14−15). However, ARO
appeared to be intolerant of substituents on the phenyl ring
ortho to boron. For example, 2-chlorophenylboronic acid and
2-methylphenylboronic acid gave products 2f and 2k in poor
yields with low ee values, respectively (Table 3, entries 6 and
11). When 4-acetylphenylboronic acid was used as the
nucleophile, no ring-opening product 2h was found because
of the highly electron-withdrawing acetyl group that reduced
the reactivity of the 4-acetylphenyl carbanion (Table 3, entry
8). It is noteworthy that the addition of methoxy- or ethoxy-
substituted phenylboronic acids to 1a was found to give better
enantioselectivities than that of methyl- and ethyl-substituted
phenylboronic acids (Table 3, entries 9, 10, 12, and 14−16).
The ARO of 1a with 3,5-dimethylphenylboronic acid also
showed high reactivity and enantioselectivity (76% yield, 81%
ee) (Table 3, entry 17), whereas the reaction of 1a with 2-
naphthylboronic acid gave product 2r in only 54% yield with
77% ee (Table 3, entry 18). Additionally, two arylboronic acids
containing heterocycle were employed in the ring-opening of
1a, but the results were unsatisfactory (Table 3, entries 19 and
20). For example, thiophene-3-boronic acid reacted with 1a and
obtained 2s in poor yield (22% yield) with modest
enantioselectivity (75% ee), whereas the ring-opening reaction
of 1a with pyridine-4-boronic acid failed to afford expected
Under the optimized conditions, the scope of arylboronic
acids was evaluated. The results of ARO of oxabenzonorborna-
diene 1a with various arylboronic acids were summarized in
Table 3. The results indicated that the structures of arylboronic
acids had a significant impact on the reactivity and
enantioselectivity. In general, arylboronic acids with electron-
withdrawing substituents led to relatively higher yields and
lower enantioselectivities (Table 3, entries 2−7), whereas
C
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product 2t even after a prolonged reaction time (Table 3, entry
20).
yield with 84% ee, respectively (Table 4, entries 8 and 9),
whereas 4-methylphenylboronic acid and 3-methylphenylbor-
onic acid afforded 4d and 4e in 81% yield with 73% ee and 71%
yield with 83% ee, respectively (Table 4, entries 10 and 11).
1,4-Epoxy-1,4-dihydrotriphenylene 1d also showed high
reactivity and excellent enantioselectivity in the ARO with
arylboronic acids under the same conditions (Table 4, entries
12−16). Ring-opening products 5a−e were formed with almost
complete conversion and satisfactory enantioselectivities. The
ARO of 1d with arylboronic acid bearing the electron-donating
group Me on the phenyl ring para to boron offered better
enantioselectivity (89% ee) than the one bearing the electron-
withdrawing group Cl (81% ee) (Table 4, entries 13 and 14). It
is also noteworthy that 4-methylphenylboronic acid performing
the ARO reaction of 1d showed the best yield and ee value
(96% yield, 89% ee) compared with phenylboronic acid (95%
yield, 85% ee), 3-methylphenylboronic acid (92% yield, 79%
ee), and 4-ethylphenylboronic acid (90% yield, 87% ee) (Table
4, entries 12 and 14−16).
The molecular configuration of 2m was unambiguously
confirmed by X-ray diffraction analysis. The single crystal was
obtained by solvent evaporation from a mixture of CHCl3,
hexane, and ethyl acetate. The configuration of 2m was
assigned as (1S,2R) and confirmed as the 1,2-cis configuration,
as shown in the Supporting Information.
The substrate scope of the oxabicyclic alkenes was also
evaluated, and the results are listed in Table 4. From Table 4,
Table 4. Scope of Platinum(II)-Catalyzed ARO Addition of
Various Arylboronic Acids to Oxabenzonorbornadienes 1b−
a
d
On the basis of these results, a proposed mechanism for the
platinum(II)-catalyzed ARO addition of phenylboronic acid to
oxabenzonorbornadiene 1a is summarized in Scheme 1. The
b
entry substrate
R
product time (h) yield (%) ee (%)
1
1b
1b
1b
1b
1b
1b
1c
1c
1c
1c
1c
1d
1d
1d
1d
1d
H
3a
3b
3c
3d
3e
3f
29
96
78
96
37
48
48
47
47
18
18
9
80
77
92
89
92
61
92
80
92
81
71
95
97
96
92
90
71
62
76
84
81
78
58
78
84
73
83
85
81
89
79
87
Scheme 1. Working Hypothesis for the Platinum(II)-
Catalyzed ARO Addition of Phenylboronic Acid to
Oxabenzonorbornadiene 1a
2
4-bromo
4-chloro
4-methyl
3-methyl
4-methoxy
H
3
4
5
6
7
4a
4b
4c
4d
4e
5a
5b
5c
5d
5e
8
4-bromo
4-chloro
4-methyl
3-methyl
H
9
10
11
12
13
14
15
16
4-chloro
4-methyl
3-methyl
4-ethyl
9
9
12
24
a
The reaction was carried out with oxabenzonorbornadiene (0.2
mmol), 3.0 equiv of arylboronic acid (0.6 mmol), and 0.5 equiv of KF
(5 M in H2O) in CH2Cl2 (2.0 mL) at 25 °C in the presence of
Pt(COD)Cl2 (2.5 mol %) and (S)-(−)-DM-SEGPHOS (2.5 mol %).
b
Determined by HPLC with a Chiralcel OD-H or Chiralpak AD-H
column.
we can see that the ARO addition of arylboronic acids to
oxabenzonorbornadienes 1b−d proceeded smoothly to give the
expected products in high yields (up to 97%) with moderate to
good enantioselectivities (up to 89% ee). The ARO of 1b with
arylboronic acids bearing an electron-rich Me group showed
better results than those bearing electron-deficient Br and Cl
groups (Table 4, entries 2−5), furnishing 3d and 3e in excellent
yields (89 and 92%, respectively) and high ee values (84 and
81% ee, respectively). However, in the case of 4-methox-
yphenylboronic acid as the nucleophile for the reaction of 1b,
the yield was decreased to 61% (Table 4, entry 6).
Furthermore, the ARO of 1c are preferred for arylboronic
acids involving electron-deficient substituents, obtaining the
corresponding products in better yields and ee values (Table 4,
entries 7−11). For example, 4-bromophenylboronic acid and 4-
chlorophenylboronic acid for the ring-opening of 1c gave ring-
opening products 4b and 4c in 80% yield with 78% ee and 92%
active catalyst of chiral platinum complex A was first formed
through replacing the ligand COD of the precatalyst
Pt(COD)Cl2 by (S)-(−)-DM-SEGPHOS.18 Then, platinum
complex B was generated by transmetalation of phenyl from
boron to platinum.11,19 This process might require a base to
activate the boron species and promote the reaction.20 Next
followed the addition of the phenyl−platinum linkage across a
carbon−carbon double bond of 1a from the exo side to give
C.13 β-Elimination of oxygen to open the furyl ring and to give
the ring-opened intermediate D occurs followed by the
hydrolysis to liberate ring-opened product 2a. Meanwhile, the
platinum(II) species A that is regenerated promotes the next
catalytic cycle.
D
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126.5, 121.3, 71.2, 46.8 ppm. (APCI-ion trap) m/z: [M − 3H]−
calcd for C16H10OBr, 296.9915, 298.9894; found, 296.9924,
298.9905.
CONCLUSIONS
■
We have successfully developed a new platinum(II)-catalyzed
ARO of oxabenzonorbornadienes with the addition of
arylboronic acids. Pt(COD)Cl2 and (S)-(−)-DM-SEGPHOS
were used as the catalyst system in ARO for the first time. The
ARO addition can proceed smoothly in the presence of
platinum catalyst. It provides a practical and efficient approach
to synthesize the optically active cis-2-aryl-1,2-dihydronaph-
thalen-1-ol derivatives in high yields with good enantioselectiv-
ities under very mild conditions. It is also noteworthy that the
addition of chiral ligands and KF have a significant impact on
the reactivity and enantioselectivity of ARO. Further inves-
tigations on the applications of platinum catalysts in
asymmetric reactions are in progress in our laboratory and
will be reported in due course.
(1S,2R)-2-(3-Bromophenyl)-1,2-dihydronaphthalen-1-ol
(2c). Prepared according to general procedure I. Colorless oil
(48 mg, 79%). Rf = 0.19 on silica gel (petroleum ether/ethyl
acetate 10:1, v/v). The ee was determined to be 46% using
HPLC analysis on a Chiralcel OD-H column (hexane/2-
propanol 90:10, 1.0 mL/min, λ = 254 nm). Retention times
were 7.8 (minor) and 10.6 min (major). [α]2D5 = +48.8 (c 1.00,
CHCl3). IR (neat): 3047 (br), 3069, 2926, 1665, 1594, 1567,
1
1473, 1068, 774 cm−1. H NMR (400 MHz, CDCl3): δ 7.44−
7.15 (m, 8H), 6.71 (dd, J = 1.6, 9.6 Hz, 1H), 6.06 (dd, J = 3.6,
9.6 Hz, 1H), 4.86 (s, 1H), 3.82−3.80 (m, 1H), 1.57 (s, 1H)
ppm. 13C NMR (100 MHz, CDCl3): δ 140.7, 135.7, 132.4,
132.3, 130.4, 130.1, 128.8, 128.6, 128.5, 128.2, 127.8, 126.8,
126.6, 122.6, 71.2, 47.1 ppm. HRMS (ESI-ion trap) m/z: [M −
3H]− calcd for C16H10OBr, 296.9915, 298.9894; found,
296.9915, 298.9894.
EXPERIMENTAL SECTION
■
General Procedure I for Platinum-Catalyzed ARO
Addition of Arylboronic Acids to Oxabenzonorborna-
dienes. A 10 mL round-bottomed flask fitted with a reflux
condenser was flame-dried under a stream of nitrogen and
cooled to room temperature. Pt(COD)Cl2 (1.9 mg, 2.5 mol %)
and (S)-(−)-DM-SEGPHOS (3.6 mg, 2.5 mol %) were
simultaneously added followed by the addition of CH2Cl2
(2.0 mL). The mixture was stirred for about 30 min before
oxabenzonorbornadiene 1 (0.2 mmol) and arylboronic acid (3
equiv) were added. Finally, KF solution (5 M in H2O, 20 μL,
0.5 equiv) was added. The resulting mixture was stirred at 25
°C until completion, as monitored by thin-layer chromatog-
raphy. The solvent was removed in vacuo, and the crude
mixture was then purified by column chromatography on silica
gel (silica gel, 200−300 mesh) to afford the target product.
(1S,2R)-2-Phenyl-1,2-dihydronaphthalen-1-ol (2a). Pre-
pared according to general procedure I. Colorless oil (40 mg,
90%). Rf = 0.21 on silica gel (petroleum ether/ethyl acetate
10:1, v/v). The ee was determined to be 82% using HPLC
analysis on a Chiralcel OD-H column (hexane/2-propanol
90:10, 1.0 mL/min, λ = 254 nm). Retention times were 8.0
(minor) and 12.2 min (major). [α]2D5 = +385.7 (c 1.00, CHCl3).
IR (neat): 3546, 3423 (br), 3030, 2920, 1601, 1493, 1451,
(1S,2R)-2-(4-Chlorophenyl)-1,2-dihydronaphthalen-1-ol
(2d). Prepared according to general procedure I. White solid
(44 mg, 86%). Rf = 0.16 on silica gel (petroleum ether/ethyl
acetate 10:1, v/v). mp 58−60 °C. The ee was determined to be
68% using HPLC analysis on a Chiralcel OD-H column
(hexane/2-propanol 90:10, 1.0 mL/min, λ = 254 nm).
Retention times were 7.8 (minor) and 11.8 min (major).
[α]2D5 = +46.3 (c 1.00, CHCl3). IR (neat): 3547, 3430 (br),
3029, 2920, 1608, 1486, 1451, 1376, 1073, 778 cm−1. 1H NMR
(400 MHz, CDCl3): δ 7.33−7.16 (m, 8H), 6.70 (d, J = 9.6 Hz,
1H), 6.06 (dd, J = 3.6, 9.2 Hz, 1H), 4.89 (d, J = 5.6 Hz, 1H),
3.82−3.80 (m, 1H), 1.53 (s, 1H) ppm. 13C NMR (100 MHz,
CDCl3): δ 136.3, 135.9, 133.2, 132.4, 130.7, 129.2, 128.7, 128.5,
128.4, 128.2, 126.6, 126.5, 71.2, 46.7 ppm. HRMS (ESI-ion
trap) m/z: [M + Cl]− calcd for C16H13OCl2, 291.0344; found,
291.0345.
(1S,2R)-2-(3-Chlorophenyl)-1,2-dihydronaphthalen-1-ol
(2e). Prepared according to general procedure I. Colorless oil
(46 mg, 90%). Rf = 0.19 on silica gel (petroleum ether/ethyl
acetate 10:1, v/v). The ee was determined to be 44% using
HPLC analysis on a Chiralcel OD-H column (hexane/2-
propanol 90:10, 1.0 mL/min, λ = 254 nm). Retention times
were 8.0 (minor) and 11.1 min (major). [α]2D5 = +140.0 (c 1.00,
CHCl3). IR (neat): 3416 (br), 3073, 2926, 1661, 1594, 1567,
1
1379, 1071, 767 cm−1. H NMR (400 MHz, CDCl3): δ 7.34−
7.22 (m, 8H), 7.17 (d, J = 7.2 Hz, 1H), 6.70 (dd, J = 1.6, 9.6
Hz, 1H), 6.12 (dd, J = 4.0, 9.6 Hz, 1H), 4.92 (d, J = 5.6 Hz,
1H), 3.88−3.85 (m, 1H), 1.53 (s, 1H) ppm. 13C NMR (100
MHz, CDCl3): δ 137.8, 136.1, 132.6, 129.7, 129.3, 128.7, 128.3,
128.2, 128.0, 127.4, 126.7, 126.4, 71.3, 47.4 ppm. HRMS
(APCI-ion trap) m/z: [M − 3H]− calcd for C16H11O,
219.0810; found, 219.0809.
1
1474, 1073, 783 cm−1. H NMR (400 MHz, CDCl3): δ 7.32−
7.11 (m, 8H), 6.70 (d, J = 9.6 Hz, 1H), 6.06 (dd, J = 4.0, 9.6
Hz, 1H), 4.85 (d, J = 4.4 Hz, 1H), 3.82−3.79 (m, 1H), 1.59 (s,
1H) ppm. 13C NMR (100 MHz, CDCl3): δ 140.3, 135.8, 134.4,
132.3, 129.8, 129.5, 128.9, 128.6, 128.5, 128.2, 127.5, 127.4,
126.8, 126.6, 71.2, 47.1 ppm. HRMS (ESI-ion trap) m/z: [M +
Cl]− calcd for C16H13OCl2, 291.0344; found, 291.0344.
(1S,2R)-2-(4-Bromophenyl)-1,2-dihydronaphthalen-1-ol
(2b). Prepared according to general procedure I. Colorless oil
(47 mg, 78%). Rf = 0.17 on silica gel (petroleum ether/ethyl
acetate 10:1, v/v). The ee was determined to be 68% using
HPLC analysis on a Chiralcel OD-H column (hexane/2-
propanol 90:10, 1.0 mL/min, λ = 254 nm). Retention times
were 7.4 (minor) and 10.8 min (major). [α]2D5 = +410.7 (c 1.00,
CHCl3). IR (neat): 3444 (br), 3043, 2925, 1661, 1488, 1073,
(1R,2S)-2-(2-Chlorophenyl)-1,2-dihydronaphthalen-1-ol
(2f). Prepared according to general procedure I. Colorless oil
(25 mg, 48%). Rf = 0.16 on silica gel (petroleum ether/ethyl
acetate 10:1, v/v). The ee was determined to be 49% using
HPLC analysis on a Chiralcel OD-H column (hexane/2-
propanol 90:10, 1.0 mL/min, λ = 254 nm). Retention times
were 8.2 (major) and 16.7 min (minor). [α]2D5 = +33.0 (c 1.00,
CHCl3). IR (neat): 3565, 3383 (br), 3035, 2924, 1473, 1434,
1
1004, 803 cm−1. H NMR (400 MHz, CDCl3): δ 7.41 (d, J =
1
8.4 Hz, 2H), 7.33−7.23 (m, 3H), 7.17 (d, J = 7.2 Hz, 1H), 7.12
(d, J = 8.4 Hz, 2H), 6.70 (dd, J = 2.0, 9.6 Hz, 1H), 6.06 (dd, J =
4.0, 9.6 Hz, 1H), 4.89 (d, J = 6.0 Hz, 1H), 3.81−3.78 (m, 1H),
1.55 (s, 1H) ppm. 13C NMR (100 MHz, CDCl3): δ 136.9,
135.9, 132.4, 131.6, 131.0, 129.1, 128.5, 128.4, 128.2, 126.6,
1371, 1307, 1036, 753 cm−1. H NMR (400 MHz, CDCl3): δ
7.44−7.19 (m, 8H), 6.74 (dd, J = 2.4, 9.6 Hz, 1H), 6.04 (dd, J =
1.6, 9.6 Hz, 1H), 4.89 (d, J = 3.2 Hz, 1H), 4.50−4.47 (m, 1H),
1.57 (s, 1H) ppm. 13C NMR (100 MHz, CDCl3): δ 136.9,
135.1, 134.2, 132.1, 131.0, 129.6, 129.1, 128.8, 128.5, 128.3,
E
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128.1, 128.0, 127.0, 126.7, 69.2, 44.0 ppm. HRMS (ESI-ion
trap) m/z: [M + Cl]− calcd for C16H13OCl2, 291.0344; found,
291.0345.
3.2, 9.6 Hz, 1H), 4.80 (t, J = 5.6 Hz, 1H), 4.19−4.17 (m, 1H),
2.42 (s, 3H), 1.54 (d, J = 6.4 Hz, 1H) ppm. 13C NMR (100
MHz, CDCl3): δ 136.8, 136.6, 135.4, 132.5, 130.7, 130.5, 129.3,
128.7, 128.0, 127.9, 127.7, 127.3, 126.6, 126.4, 69.6, 43.2, 19.9
ppm. HRMS (ESI-ion trap) m/z: [M + Na]+ calcd for
C17H16ONa, 259.1099; found, 259.1090.
(1S,2R)-2-(4-Fluorophenyl)-1,2-dihydronaphthalen-1-ol
(2g). Prepared according to general procedure I. White solid
(40 mg, 84%). Rf = 0.19 on silica gel (petroleum ether/ethyl
acetate 10:1, v/v). mp 59−60 °C. The ee was determined to be
75% using HPLC analysis on a Chiralcel OD-H column
(hexane/2-propanol 90:10, 1.0 mL/min, λ = 254 nm).
Retention times were 7.1 (minor) and 11.4 min (major).
[α]2D5 = +149.5 (c 1.00, CHCl3). IR (neat): 3560, 3396 (br),
3033, 2923, 1657, 1602, 1508, 1451, 1222, 806 cm−1. 1H NMR
(400 MHz, CDCl3): δ 7.32−7.15 (m, 6H), 6.97 (t, J = 8.4 Hz,
2H), 6.69 (d, J = 9.6 Hz, 1H), 6.07 (dd, J = 4.0, 9.6 Hz, 1H),
4.88 (t, J = 6.4 Hz, 1H), 3.81 (s, 1H), 1.55 (d, J = 8.0 Hz, 1H)
(1S,2R)-2-(4-Ethylphenyl)-1,2-dihydronaphthalen-1-ol (2l).
Prepared according to general procedure I. Colorless oil (31
mg, 61%). Rf = 0.25 on silica gel (petroleum ether/ethyl acetate
10:1, v/v). The ee was determined to be 85% using HPLC
analysis on a Chiralcel OD-H column (hexane/2-propanol
90:10, 1.0 mL/min, λ = 254 nm). Retention times were 5.7
(minor) and 9.0 min (major). [α]2D5 = +248.4 (c 1.00, CHCl3).
IR (neat): 3558, 3429 (br), 3026, 2962, 2926, 1665, 1512,
1451, 1378, 1072, 839, 809 cm−1. 1H NMR (400 MHz,
CDCl3): δ 7.34−7.12 (m, 8H), 6.68 (d, J = 9.6 Hz, 1H), 6.11
(dd, J = 3.2, 9.6 Hz, 1H), 4.91 (d, J = 5.2 Hz, 1H), 3.83 (s, 1H),
2.61 (q, J = 7.6 Hz, 2H), 1.54 (s, 1H), 1.21 (t, J = 7.6 Hz, 3H)
ppm. 13C NMR (100 MHz, CDCl3): δ 143.4, 136.2, 134.7,
132.7, 130.0, 129.2, 128.3, 128.2, 128.1, 128.0, 126.7, 126.3,
71.3, 47.0, 28.5, 15.5 ppm. HRMS (ESI-ion trap) m/z: [M +
Na]+ calcd for C18H18ONa, 273.1255; found, 273.1246.
1
ppm. 13C NMR (100 MHz, CDCl3): δ 162.2 (d, JCF = 244.1
Hz), 136.0, 133.3 (d, 4JCF = 3.1 Hz), 132.5, 130.8 (d, 3JCF = 7.9
2
Hz), 129.6, 128.4, 128.3, 128.2, 126.6, 126.5, 115.4 (d, JCF
=
21.1 Hz), 71.3, 46.5 ppm. 19F NMR (376 MHz, CDCl3): δ
−115.33, −115.41 (m) ppm. HRMS (ESI-ion trap) m/z: [M +
Na]+ calcd for C16H13OFNa, 263.0848; found, 263.0842.
(1S,2R)-2-(4-Methylphenyl)-1,2-dihydronaphthalen-1-ol
(2i). Prepared according to general procedure I. Colorless oil
(40 mg, 84%). Rf = 0.20 on silica gel (petroleum ether/ethyl
acetate 10:1, v/v). The ee was determined to be 82% using
HPLC analysis on a Chiralcel OD-H column (hexane/2-
propanol 90:10, 1.0 mL/min, λ = 254 nm). Retention times
were 6.4 (minor) and 9.3 min (major). [α]2D5 = +183.3 (c 1.00,
CHCl3). IR (neat): 3546, 3435 (br), 3030, 2919, 1510, 1485,
(1S,2R)-2-(4-tert-Butylphenyl)-1,2-dihydronaphthalen-1-ol
(2m). Prepared according to general procedure I. White solid
(39 mg, 70%). Rf = 0.31 on silica gel (petroleum ether/ethyl
acetate 10:1, v/v). mp 122−124 °C. The ee was determined to
be 82% using HPLC analysis on a Chiralcel OD-H column
(hexane/2-propanol 90:10, 1.0 mL/min, λ = 254 nm).
Retention times were 5.2 (minor) and 10.5 min (major).
[α]2D5 = +217.0 (c 1.00, CHCl3). IR (neat): 3558, 3421 (br),
3028, 2957, 2922, 1668, 1480, 1367, 1269, 1073, 810, 765
1
1452, 1375, 1071, 790 cm−1. H NMR (400 MHz, CDCl3): δ
7.34−7.10 (m, 8H), 6.68 (dd, J = 1.2, 9.6 Hz, 1H), 6.11 (dd, J =
4.0, 9.6 Hz, 1H), 4.91 (d, J = 4.8 Hz, 1H), 3.84−3.81 (m, 1H),
2.31 (s, 3H), 1.53 (s, 1H) ppm. 13C NMR (100 MHz, CDCl3):
δ 137.1, 136.2, 134.4, 132.7, 129.9, 129.4, 129.1, 128.2, 128.1,
128.0, 126.7, 126.3, 71.3, 46.9, 21.1 ppm. HRMS (ESI-ion trap)
m/z: [M + Na]+ calcd for C17H16ONa, 259.1099; found,
259.1090.
1
cm−1. H NMR (400 MHz, CDCl3): δ 7.36−7.15 (m, 8H),
6.68 (d, J = 9.6 Hz, 1H), 6.12 (dd, J = 4.0, 9.6 Hz, 1H), 4.92 (s,
1H), 3.85−3.83 (m, 1H), 1.55 (s, 1H), 1.30 (s, 9H) ppm. 13C
NMR (100 MHz, CDCl3): δ 150.3, 136.2, 134.5, 132.7, 130.0,
128.9, 128.3, 128.0, 127.9, 126.7, 126.4, 125.7, 71.3, 46.9, 34.5,
31.4 ppm. HRMS (ESI-ion trap) m/z: [M + Na]+ calcd for
C20H22ONa, 301.1568; found, 301.1559.
(1S,2R)-2-(3-Methylphenyl)-1,2-dihydronaphthalen-1-ol
(2j). Prepared according to general procedure I. Colorless oil
(42 mg, 90%). Rf = 0.20 on silica gel (petroleum ether/ethyl
acetate 10:1, v/v). The ee was determined to be 80% using
HPLC analysis on a Chiralcel OD-H column (hexane/2-
propanol 90:10, 1.0 mL/min, λ = 254 nm). Retention times
were 6.7 (minor) and 8.8 min (major). [α]2D5 = +170.9 (c 1.00,
CHCl3). IR (neat): 3547, 3425 (br), 3031, 2920, 1606, 1488,
(1S,2R)-2-(4-Methoxyphenyl)-1,2-dihydronaphthalen-1-ol
(2n). Prepared according to general procedure I. Colorless oil
(26 mg, 51%). Rf = 0.10 on silica gel (petroleum ether/ethyl
acetate 10:1, v/v). The ee was determined to be 87% using
HPLC analysis on a Chiralcel OD-H column (hexane/2-
propanol 90:10, 1.0 mL/min, λ = 254 nm). Retention times
were 9.6 (minor) and 15.4 min (major). [α]2D5 = +324.0 (c 1.00,
CHCl3). IR (neat): 3552, 3458 (br), 3032, 2926, 1613, 1510,
1
1452, 1378, 1072, 777 cm−1. H NMR (400 MHz, CDCl3): δ
1
7.35−7.16 (m, 5H), 7.10−7.05 (m, 3H), 6.70 (dd, J = 2.4, 10.0
Hz, 1H), 6.11 (dd, J = 3.6, 9.6 Hz, 1H), 4.89 (t, J = 4.8 Hz,
1H), 3.85−3.82 (m, 1H), 2.33 (s, 3H), 1.53 (d, J = 6.4 Hz, 1H)
ppm. 13C NMR (100 MHz, CDCl3): δ 138.3, 137.8, 136.0,
132.6, 130.0, 129.7, 128.6, 128.4, 128.2, 128.1, 128.0, 126.9,
126.4, 126.1, 71.3, 47.3, 21.5 ppm. HRMS (ESI-ion trap) m/z:
[M + Na]+ calcd for C17H16ONa, 259.1099; found, 259.1091.
(1S,2R)-2-(2-Methylphenyl)-1,2-dihydronaphthalen-1-ol
(2k). Prepared according to general procedure I. Colorless oil
(9 mg, 20%). Rf = 0.16 on silica gel (petroleum ether/ethyl
acetate 10:1, v/v). The ee was determined to be 11% using
HPLC analysis on a Chiralcel OD-H column (hexane/2-
propanol 90:10, 1.0 mL/min, λ = 254 nm). Retention times
were 7.5 (minor) and 12.5 min (major). [α]2D5 = +443.5 (c 1.00,
CHCl3). IR (neat): 3533, 3405 (br), 3029, 2926, 1668, 1481,
1411, 1249, 1179, 1030, 805 cm−1. H NMR (400 MHz,
CDCl3): δ 7.35 (d, J = 6.8 Hz, 1H), 7.30−7.22 (m, 2H), 7.16
(d, J = 7.6 Hz, 3H), 6.84 (d, J = 8.0 Hz, 2H), 6.68 (d, J = 9.6
Hz, 1H), 6.10 (dd, J = 4.0, 9.6 Hz, 1H), 4.93 (s, 1H), 3.81 (s,
1H), 3.77 (s, 3H), 1.51 (s, 1H) ppm. 13C NMR (100 MHz,
CDCl3): δ 159.0, 136.3, 132.7, 130.3, 130.1, 129.1, 128.2, 128.1,
128.0, 126.5, 126.3, 114.1, 71.3, 55.3, 46.4 ppm. HRMS (ESI-
ion trap) m/z: [M + Na]+ calcd for C17H16O2Na, 275.1048;
found, 275.1038.
(1S,2R)-2-(3-Methoxyphenyl)-1,2-dihydronaphthalen-1-ol
(2o). Prepared according to general procedure I. Colorless oil
(31 mg, 61%). Rf = 0.10 on silica gel (petroleum ether/ethyl
acetate 10:1, v/v). The ee was determined to be 81% using
HPLC analysis on a Chiralcel OD-H column (hexane/2-
propanol 90:10, 1.0 mL/min, λ = 254 nm). Retention times
were 10.4 (minor) and 14.9 min (major). [α]2D5 = +233.6 (c
1.00, CHCl3). IR (neat): 3439 (br), 3354, 3032, 2917, 1660,
1
1463, 1378, 1072, 765 cm−1. H NMR (400 MHz, CDCl3): δ
7.34−7.15 (m, 8H), 6.70 (dd, J = 2.4, 9.6 Hz, 1H), 6.06 (dd, J =
F
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The Journal of Organic Chemistry
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1595, 1483, 1455, 1253, 1044, 772 cm−1. 1H NMR (400 MHz,
CDCl3): δ 7.34 (d, J = 7.2 Hz, 1H), 7.30−7.21 (m, 3H), 7.16
(d, J = 7.2 Hz, 1H), 6.86 (d, J = 7.6 Hz, 1H), 6.81−6.80 (m,
2H), 6.69 (dd, J = 1.6, 9.6 Hz, 1H), 6.11 (dd, J = 4.0, 9.6 Hz,
1H), 4.92 (d, J = 5.6 Hz, 1H), 3.85−3.82 (m, 1H), 3.73 (s,
3H), 1.57 (s, 1H) ppm. 13C NMR (100 MHz, CDCl3): δ 159.8,
139.3, 136.1, 132.6, 129.6, 129.5, 128.3, 128.2, 128.0, 126.7,
126.4, 121.5, 114.8, 112.9, 71.3, 55.1, 47.4 ppm. HRMS (ESI-
ion trap) m/z: [M + Na]+ calcd for C17H16O2Na, 275.1048;
found, 275.1038.
HPLC analysis on a Chiralcel OD-H column (hexane/2-
propanol 95:5, 1.0 mL/min, λ = 254 nm). Retention times were
14.3 (minor) and 21.9 min (major). [α]2D5 = +416.0 (c 1.00,
CHCl3). IR (neat): 3546, 3410 (br), 3034, 2923, 1663, 1506,
1
1396, 1295, 1077, 788 cm−1. H NMR (400 MHz, CDCl3): δ
7.37 (d, J = 6.8 Hz, 1H), 7.31−7.23 (m, 3H), 7.15 (d, J = 6.8
Hz, 2H), 6.90 (d, J = 4.8 Hz, 1H), 6.65 (d, J = 9.6 Hz, 1H),
6.12 (dd, J = 4.4, 9.6 Hz, 1H), 4.97 (t, J = 6.4 Hz, 1H), 3.97 (t, J
= 4.4 Hz, 1H), 1.62 (d, J = 8.0 Hz, 1H) ppm. 13C NMR (100
MHz, CDCl3): δ 138.0, 136.4, 132.6, 129.5, 128.2, 128.1, 127.9,
126.3, 126.2, 126.1, 123.1, 70.9, 42.7 ppm. HRMS (ESI-ion
trap) m/z: [M + Na]+ calcd for C14H12OSNa, 251.0507; found,
251.0496.
(1S,2R)-2-(4-Ethoxyphenyl)-1,2-dihydronaphthalen-1-ol
(2p). Prepared according to general procedure I. Colorless oil
(33 mg, 62%). Rf = 0.12 on silica gel (petroleum ether/ethyl
acetate 10:1, v/v). The ee was determined to be 89% using
HPLC analysis on a Chiralcel OD-H column (hexane/2-
propanol 90:10, 1.0 mL/min, λ = 254 nm). Retention times
were 7.9 (minor) and 11.9 min (major). [α]2D5 = +298.6 (c 1.00,
CHCl3). IR (neat): 3551, 3438 (br), 3033, 2977, 2923, 1610,
(1S,2R)-6,7-Dibromo-2-phenyl-1,2-dihydronaphthalen-1-
ol (3a). Prepared according to general procedure I. Colorless
oil (61 mg, 80%). Rf = 0.18 on silica gel (petroleum ether/ethyl
acetate 10:1, v/v). The ee was determined to be 71% using
HPLC analysis on a Chiralcel OD-H column (hexane/2-
propanol 90:10, 1.0 mL/min, λ = 254 nm). Retention times
were 8.8 (minor) and 11.1 min (major). [α]2D5 = −104.2 (c 1.00,
CHCl3). IR (neat): 3517, 3338 (br), 3026, 2919, 1664, 1490,
1
1513, 1480, 1396, 1248, 1177, 1049, 808 cm−1. H NMR (400
MHz, CDCl3): δ 7.34 (d, J = 6.8 Hz, 1H), 7.30−7.21 (m, 2H),
7.16−7.13 (m, 3H), 6.82 (d, J = 8.4 Hz, 2H), 6.67 (d, J = 9.6
Hz, 1H), 6.10 (dd, J = 4.0, 9.2 Hz, 1H), 4.91 (s, 1H), 3.99 (q, J
= 6.8 Hz, 2H), 3.81−3.79 (m, 1H), 1.52 (s, 1H), 1.38 (t, J = 7.2
Hz, 3H) ppm. 13C NMR (100 MHz, CDCl3): δ 158.4, 136.3,
132.7, 130.3, 130.1, 128.9, 128.2, 128.0, 127.9, 126.5, 126.3,
114.7, 71.3, 63.4, 46.4, 14.9 ppm. HRMS (ESI-ion trap) m/z:
[M + Na]+ calcd for C18H18O2Na, 289.1205; found, 289.1194.
(1S,2R)-2-(3,5-Dimethylphenyl)-1,2-dihydronaphthalen-1-
ol (2q). Prepared according to general procedure I. Colorless
oil (38 mg, 76%). Rf = 0.26 on silica gel (petroleum ether/ethyl
acetate 10:1, v/v). The ee was determined to be 81% using
HPLC analysis on a Chiralcel OD-H column (hexane/2-
propanol 90:10, 1.0 mL/min, λ = 254 nm). Retention times
were 5.6 (minor) and 7.6 min (major). [α]2D5 = +126.7 (c 1.00,
CHCl3). IR (neat): 3542, 3429 (br), 3029, 2922, 1599, 1452,
1
1465, 1383, 887, 701 cm−1. H NMR (400 MHz, CDCl3): δ
7.57 (s, 1H), 7.40 (s, 1H), 7.29 (s, 3H), 7.18 (s, 2H), 6.60 (d, J
= 9.6 Hz, 1H), 6.20 (dd, J = 4.4, 9.2 Hz, 1H), 4.96 (d, J = 5.6
Hz, 1H), 3.82 (s, 1H), 1.58 (s, 1H) ppm. 13C NMR (100 MHz,
CDCl3): δ 137.1, 135.6, 133.5, 131.8, 131.5, 130.8, 129.3, 128.9,
127.9, 126.4, 124.0, 123.6, 70.3, 46.7 ppm. HRMS (ESI-ion
trap) m/z: [M − 3H]− calcd for C16H9OBr2, 376.9000; found,
376.9013.
(1S,2R)-6,7-Dibromo-2-(4-bromophenyl)-1,2-dihydro-
naphthalen-1-ol (3b). Prepared according to general proce-
dure I. Colorless oil (71 mg, 77%). Rf = 0.17 on silica gel
(petroleum ether/ethyl acetate 10:1, v/v). The ee was
determined to be 62% using HPLC analysis on a Chiralcel
OD-H column (hexane/2-propanol 95:5, 1.0 mL/min, λ = 254
nm). Retention times were 10.7 (minor) and 12.4 min (major).
[α]2D5 = +28.6 (c 1.00, CHCl3). IR (neat): 3372 (br), 2928,
2852, 1666, 1486, 1466, 1392, 1074, 1010 cm−1. 1H NMR (400
MHz, CDCl3): δ 7.58 (s, 1H), 7.44−7.41 (m, 3H), 7.05 (d, J =
8.0 Hz, 2H), 6.61 (d, J = 9.6 Hz, 1H), 6.17 (dd, J = 4.8, 9.6 Hz,
1H), 4.97 (t, J = 7.2 Hz, 1H), 3.79 (t, J = 5.2 Hz, 1H), 1.48 (d, J
= 8.8 Hz, 1H) ppm. 13C NMR (100 MHz, CDCl3): δ 136.8,
134.8, 133.3, 131.9, 131.4, 131.2, 131.0, 130.9, 126.7, 124.2,
123.8, 121.9, 70.1, 46.1 ppm. HRMS (ESI-ion trap) m/z: [M −
3H]− calcd for C16H8OBr3, 454.8105, 456.8084; found,
454.8100, 456.8079.
1
1376, 1258, 1073, 810 cm−1. H NMR (400 MHz, CDCl3): δ
7.34−7.22 (m, 3H), 7.16 (d, J = 7.2 Hz, 1H), 6.90 (s, 3H), 6.69
(d, J = 9.6 Hz, 1H), 6.10 (dd, J = 2.8, 8.8 Hz, 1H), 4.84 (s, 1H),
3.82−3.79 (m, 1H), 2.28 (s, 6H), 1.55 (s, 1H) ppm. 13C NMR
(100 MHz, CDCl3): δ 138.3, 137.9, 136.0, 132.7, 129.8, 129.1,
128.4, 128.1, 127.9, 127.1, 126.9, 126.4, 71.3, 47.3, 21.4 ppm.
HRMS (ESI-ion trap) m/z: [M + Na]+ calcd for C18H18ONa,
273.1255; found, 273.1239.
(1S,2R)-2-Naphthyl-1,2-dihydronaphthalen-1-ol (2r). Pre-
pared according to general procedure I. Colorless oil (29 mg,
54%). Rf = 0.19 on silica gel (petroleum ether/ethyl acetate
10:1, v/v). The ee was determined to be 77% using HPLC
analysis on a Chiralcel OD-H column (hexane/2-propanol
90:10, 1.0 mL/min, λ = 254 nm). Retention times were 12.4
(minor) and 15.1 min (major). [α]2D5 = +186.6 (c 1.00, CHCl3).
IR (neat): 3549, 3432 (br), 3053, 2923, 1599, 1507, 1451,
(1S,2R)-6,7-Dibromo-2-(4-chlorophenyl)-1,2-dihydronaph-
thalen-1-ol (3c). Prepared according to general procedure I.
Colorless oil (76 mg, 92%). Rf = 0.17 on silica gel (petroleum
ether/ethyl acetate 10:1, v/v). The ee was determined to be
76% using HPLC analysis on a Chiralcel OD-H column
(hexane/2-propanol 95:5, 1.0 mL/min, λ = 254 nm). Retention
times were 9.9 (minor) and 11.8 min (major). [α]2D5 = +167.7
(c 1.00, CHCl3). IR (neat): 3545, 3376 (br), 3041, 2922, 1665,
1
1377, 1072, 791 cm−1. H NMR (400 MHz, CDCl3): δ 7.76−
7.71 (m, 4H), 7.45−7.40 (m, 2H), 7.31−7.16 (m, 5H), 6.72 (d,
J = 9.6 Hz, 1H), 6.17 (dd, J = 3.6, 9.6 Hz, 1 H), 4.94 (s, 1H),
3.97−3.95 (m, 1H), 1.58 (d, J = 6.0 Hz, 1H) ppm. 13C NMR
(100 MHz, CDCl3): δ 136.1, 135.4, 133.5, 132.8, 132.7, 129.6,
128.5, 128.4, 128.3, 128.2, 128.1, 127.8, 127.7, 127.4, 126.8,
126.5, 126.2, 125.9, 71.3, 47.5 ppm. HRMS (ESI-ion trap) m/z:
[M + Na]+ calcd for C20H16ONa, 295.1099; found, 295.1089.
(1S,2R)-2-(Thiophen-3-yl)-1,2-dihydronaphthalen-1-ol
(2s). Prepared according to general procedure I. Colorless oil
(10 mg, 22%). Rf = 0.22 on silica gel (petroleum ether/ethyl
acetate 10:1, v/v). The ee was determined to be 75% using
1
1590, 1487, 1465, 1269, 1086, 1015, 886 cm−1. H NMR (400
MHz, CDCl3): δ 7.54 (s, 1H), 7.39 (s, 1H), 7.25 (d, J = 7.6 Hz,
2H), 7.08 (d, J = 7.6 Hz, 2H), 6.59 (d, J = 9.6 Hz, 1H), 6.15
(dd, J = 4.8, 9.6 Hz, 1H), 4.91 (d, J = 5.6 Hz, 1H), 3.77 (t, J =
5.6 Hz, 1H), 1.62 (s, 1H) ppm. 13C NMR (100 MHz, CDCl3):
δ 136.8, 134.3, 133.7, 133.3, 131.4, 131.3, 130.9, 130.7, 128.9,
126.7, 124.2, 123.8, 70.2, 46.1 ppm. HRMS (ESI-ion trap) m/z:
[M − 3H]− calcd for C16H8OBr2Cl, 410.8610; found,
410.8605.
G
dx.doi.org/10.1021/jo402386k | J. Org. Chem. XXXX, XXX, XXX−XXX

The Journal of Organic Chemistry
Article
(1S,2R)-6,7-Dibromo-2-(4-methylphenyl)-1,2-dihydro-
naphthalen-1-ol (3d). Prepared according to general proce-
dure I. Colorless oil (70 mg, 89%). Rf = 0.26 on silica gel
(petroleum ether/ethyl acetate 10:1, v/v). The ee was
determined to be 84% using HPLC analysis on a Chiralcel
OD-H column (hexane/2-propanol 95:5, 1.0 mL/min, λ = 254
nm). Retention times were 8.4 (minor) and 9.4 min (major).
[α]2D5 = +155.1 (c 1.00, CHCl3). IR (neat): 3545, 3385 (br),
2922, 2855, 1665, 1509, 1465, 1376, 1077, 886 cm−1. 1H NMR
(400 MHz, CDCl3): δ 7.57 (s, 1H), 7.39 (s, 1H), 7.07 (q, J =
7.6 Hz, 4H), 6.57 (d, J = 9.6 Hz, 1H), 6.18 (dd, J = 4.8, 9.6 Hz,
1H), 4.95 (d, J = 2.8 Hz, 1H), 3.78 (t, J = 5.2 Hz, 1H), 2.30 (s,
3H), 1.55 (s, 1H) ppm. 13C NMR (100 MHz, CDCl3): δ 137.7,
137.3, 133.6, 132.2, 132.0, 131.4, 130.7, 129.6, 129.2, 126.2,
123.9, 123.6, 70.2, 46.3, 21.0 ppm. HRMS (ESI-ion trap) m/z:
[M − 3H]− calcd for C17H11OBr2, 390.9156; found, 390.9151.
(1S,2R)-6,7-Dibromo-2-(3-methylphenyl)-1,2-dihydro-
naphthalen-1-ol (3e). Prepared according to general proce-
dure I. Colorless oil (73 mg, 92%). Rf = 0.26 on silica gel
(petroleum ether/ethyl acetate 10:1, v/v). The ee was
determined to be 81% using HPLC analysis on a Chiralcel
OD-H column (hexane/2-propanol 90:10, 1.0 mL/min, λ =
254 nm). Retention times were 5.2 (minor) and 7.2 min
(major). [α]2D5 = +139.6 (c 1.00, CHCl3). IR (neat): 3542, 3425
(br), 3033, 2922, 1603, 1574, 1465, 1376, 1073, 886, 774 cm−1.
1H NMR (400 MHz, CDCl3): δ 7.57 (s, 1H), 7.39 (s, 1H), 7.17
(t, J = 7.6 Hz, 1H), 7.08 (d, J = 7.6 Hz, 1H), 7.00 (s, 1H), 6.95
(d, J = 7.6 Hz, 1H), 6.58 (d, J = 9.6 Hz, 1H), 6.18 (dd, J = 4.4,
9.6 Hz, 1H), 4.91 (d, J = 6.0 Hz, 1H), 3.78 (t, J = 4.8 Hz, 1H),
2.31 (s, 3H), 1.58 (s, 1H) ppm. 13C NMR (100 MHz, CDCl3):
δ 138.6, 137.1, 135.7, 133.5, 131.8, 131.6, 130.8, 130.1, 128.8,
128.7, 126.3, 126.1, 124.0, 123.5, 70.2, 46.7, 21.5 ppm. HRMS
(ESI-ion trap) m/z: [M − 3H]− calcd for C17H11OBr2,
390.9156; found, 390.9148.
129.1, 128.9, 128.6, 127.0, 124.2, 122.5, 122.1, 111.4, 110.9,
64.3, 56.2, 56.1, 47.3 ppm. HRMS (ESI-ion trap) m/z: [M +
Na]+ calcd for C18H18O3Na, 305.1154; found, 305.1144.
(1S,2R)-5,8-Dimethoxy-2-(4-bromophenyl)-1,2-dihydro-
naphthalen-1-ol (4b). Prepared according to general proce-
dure I. White solid (58 mg, 80%). Rf = 0.11 on silica gel
(petroleum ether/ethyl acetate 10:1, v/v). mp 112−114 °C.
The ee was determined to be 78% using HPLC analysis on a
Chiralcel OD-H column (hexane/2-propanol 90:10, 1.0 mL/
min, λ = 254 nm). Retention times were 20.2 (minor) and 30.5
min (major). [α]2D5 = +20.7 (c 1.00, CHCl3). IR (neat): 3573,
1
3463 (br), 2935, 1597, 1488, 1462, 1259, 1086, 801 cm−1. H
NMR (400 MHz, CDCl3): δ 7.49 (d, J = 7.2 Hz, 2H), 7.29 (d, J
= 7.6 Hz, 2H), 7.08 (d, J = 9.6 Hz, 1H), 6.80 (q, J = 9.2 Hz,
2H), 6.05 (d, J = 9.6 Hz, 1H), 5.05 (s, 1H), 3.81 (d, J = 6.8 Hz,
6H), 3.72 (s, 1H), 1.65 (s, 1H) ppm. 13C NMR (100 MHz,
CDCl3): δ 150.6, 149.6, 139.6, 131.5, 130.9, 128.3, 124.2, 122.3,
122.2, 120.8, 111.4, 111.0, 64.2, 56.2, 56.1, 46.7 ppm. HRMS
(ESI-ion trap) m/z: [M + Na]+ calcd for C18H17O3BrNa,
383.0259, 385.0238; found, 383.0252, 385.0230.
(1S,2R)-5,8-Dimethoxy-2-(4-chlorophenyl)-1,2-dihydro-
naphthalen-1-ol (4c). Prepared according to general procedure
I. White solid (58 mg, 92%). Rf = 0.11 on silica gel (petroleum
ether/ethyl acetate 10:1, v/v). mp 96−98 °C. The ee was
determined to be 84% using HPLC analysis on a Chiralcel OD-
H column (hexane/2-propanol 90:10, 1.0 mL/min, λ = 254
nm). Retention times were 19.0 (minor) and 29.6 min (major).
[α]2D5 = −30.4 (c 1.00, CHCl3). IR (neat): 3467 (br), 2935,
1599, 1483, 1462, 1259, 1088, 804 cm−1. 1H NMR (400 MHz,
CDCl3): δ 7.34 (s, 4H), 7.08 (dd, J = 2.8, 10.0 Hz, 1H), 6.80
(q, J = 9.2 Hz, 2H), 6.05 (d, J = 10.0 Hz, 1H), 5.05 (s, 1H),
3.81 (d, J = 7.6 Hz, 6H), 3.73 (s, 1H), 1.66 (s, 1H) ppm. 13C
NMR (100 MHz, CDCl3): δ 150.6, 149.6, 139.1, 132.7, 130.6,
128.6, 128.4, 124.2, 122.3, 122.2, 111.4, 111.0, 64.3, 56.2, 56.1,
46.6 ppm. HRMS (ESI-ion trap) m/z: [M + Na]+ calcd for
C18H17O3ClNa, 339.0764; found, 339.0752.
(1S,2R)-5,8-Dimethoxy-2-(4-methylphenyl)-1,2-dihydro-
naphthalen-1-ol (4d). Prepared according to general proce-
dure I. Colorless oil (48 mg, 81%). Rf = 0.12 on silica gel
(petroleum ether/ethyl acetate 10:1, v/v). The ee was
determined to be 73% using HPLC analysis on a Chiralcel
OD-H column (hexane/2-propanol 90:10, 1.0 mL/min, λ =
254 nm). Retention times were 13.0 (minor) and 20.7 min
(major). [α]2D5 = −69.2 (c 1.00, CHCl3). IR (neat): 3487 (br),
2929, 1600, 1514, 1483, 1462, 1259, 1088, 801 cm−1. 1H NMR
(400 MHz, CDCl3): δ 7.31 (d, J = 7.6 Hz, 2H), 7.20 (d, J = 7.6
Hz, 2H), 7.08 (dd, J = 3.2, 10.0 Hz, 1H), 6.80 (q, J = 8.8 Hz,
2H), 6.12 (d, J = 10.0 Hz, 1H), 5.06 (s, 1H), 3.81 (d, J = 4.4
Hz, 6H), 3.77−3.74 (m, 1H), 2.36 (s, 3H), 1.61 (s, 1H) ppm.
13C NMR (100 MHz, CDCl3): δ 150.7, 149.6, 137.2, 136.6,
129.3, 129.2, 129.0, 124.3, 122.6, 122.0, 111.4, 110.9, 64.4, 56.2,
56.1, 46.8, 21.1 ppm. HRMS (ESI-ion trap) m/z: [M + Na]+
calcd for C19H20O3Na, 319.1310; found, 319.1300.
(1S,2R)-5,8-Dimethoxy-2-(3-methylphenyl)-1,2-dihydro-
naphthalen-1-ol (4e). Prepared according to general proce-
dure I. Colorless oil (42 mg, 71%). Rf = 0.14 on silica gel
(petroleum ether/ethyl acetate 10:1, v/v). The ee was
determined to be 83% using HPLC analysis on a Chiralcel
OD-H column (hexane/2-propanol 90:10, 1.0 mL/min, λ =
254 nm). Retention times were 12.8 (minor) and 18.4 min
(major). [α]2D5 = +37.0 (c 1.00, CHCl3). IR (neat): 3546, 3457
(br), 2919, 1596, 1482, 1457, 1258, 1086 cm−1. 1H NMR (400
MHz, CDCl3): δ 7.31−7.23 (m, 3H), 7.13 (d, J = 7.2 Hz, 1H),
(1S,2R)-6,7-Dibromo-2-(4-methoxyphenyl)-1,2-dihydro-
naphthalen-1-ol (3f). Prepared according to general procedure
I. Colorless oil (50 mg, 61%). Rf = 0.09 on silica gel (petroleum
ether/ethyl acetate 10:1, v/v). The ee was determined to be
78% using HPLC analysis on a Chiralcel OD-H column
(hexane/2-propanol 95:5, 1.0 mL/min, λ = 254 nm). Retention
times were 13.8 (minor) and 15.0 min (major). [α]2D5 = +119.3
(c 1.00, CHCl3). IR (neat): 3419 (br), 2925, 1668, 1608, 1510,
1464, 1250, 1178, 1034 cm−1. 1H NMR (400 MHz, CDCl3): δ
7.58 (s, 1H), 7.39 (s, 1H), 7.06 (d, J = 8.4 Hz, 1H), 6.82 (d, J =
8.0 Hz, 1H), 6.57 (d, J = 9.6 Hz, 1H), 6.18 (dd, J = 4.8, 9.6 Hz,
1H), 4.95 (d, J = 6.4 Hz, 1H), 3.78 (s, 1H), 3.76 (s, 3H), 1.57
(s, 1H) ppm. 13C NMR (100 MHz, CDCl3): δ 159.3, 137.3,
133.6, 132.2, 131.3, 130.7, 130.4, 126.9, 126.1, 123.9, 123.6,
114.3, 70.2, 55.3, 45.7 ppm. HRMS (ESI-ion trap) m/z: [M −
3H]− calcd for C17H11O2Br2, 406.9105; found, 406.9106.
(1S,2R)-5,8-Dimethoxy-2-phenyl-1,2-dihydronaphthalen-
1-ol (4a). Prepared according to general procedure I. Colorless
oil (52 mg, 92%). Rf = 0.13 on silica gel (petroleum ether/ethyl
acetate 10:1, v/v). The ee was determined to be 58% using
HPLC analysis on a Chiralcel OD-H column (hexane/2-
propanol 90:10, 1.0 mL/min, λ = 254 nm). Retention times
were 15.5 (minor) and 24.9 min (major). [α]2D5 = −93.5 (c 1.00,
CHCl3). IR (neat): 3567, 3472 (br), 2936, 1597, 1483, 1453,
1
1259, 1091 cm−1. H NMR (400 MHz, CDCl3): δ 7.43−7.37
(m, 4H), 7.30 (t, J = 6.8 Hz, 1H), 7.09 (dd, J = 2.8, 10.0 Hz,
1H), 6.80 (q, J = 8.8 Hz, 2H), 6.14 (d, J = 9.6 Hz, 1H), 5.08 (d,
J = 3.2 Hz, 1H), 3.81 (d, J = 5.6 Hz, 6H), 3.79 (s, 1H), 1.63 (s,
1H) ppm. 13C NMR (100 MHz, CDCl3): δ 150.7, 149.6, 140.4,
H
dx.doi.org/10.1021/jo402386k | J. Org. Chem. XXXX, XXX, XXX−XXX

The Journal of Organic Chemistry
Article
7.09 (dd, J = 3.2, 9.6 Hz, 1H), 6.82 (q, J = 9.2 Hz, 2H), 6.15
(dd, J = 1.6, 10.0 Hz, 1H), 5.08 (s, 1H), 3.83 (d, J = 2.8 Hz,
6H), 3.78−3.76 (m, 1H), 2.39 (s, 3H), 1.58 (s, 1H) ppm. 13C
NMR (100 MHz, CDCl3): δ 150.7, 149.6, 140.2, 138.2, 129.8,
129.0, 128.5, 127.8, 126.1, 124.2, 122.6, 122.0, 111.4, 110.8,
64.3, 56.2, 56.1, 47.2, 21.5 ppm. HRMS (ESI-ion trap) m/z: [M
+ Na]+ calcd for C19H20O3Na, 319.1310; found, 319.1295.
(1S,2R)-2-Phenyl-1,2-dihydrotriphenylen-1-ol (5a). Pre-
pared according to general procedure I. Colorless oil (61 mg,
95%). Rf = 0.23 on silica gel (petroleum ether/ethyl acetate
10:1, v/v). The ee was determined to be 85% using HPLC
analysis on a Chiralpak AD-H column (hexane/2-propanol
90:10, 1.0 mL/min, λ = 254 nm). Retention times were 58.1
(minor) and 62.6 min (major). [α]2D5 = −155.3 (c 1.00,
CHCl3). IR (neat): 3548, 3407 (br), 3022, 2923, 1668, 1495,
propanol 90:10, 1.0 mL/min, λ = 254 nm). Retention times
were 24.5 (minor) and 41.1 min (major). [α]2D5 = +153.7 (c
1.00, CHCl3). IR (neat): 3463 (br), 3362, 3055, 2921, 1663,
1602, 1448, 1375, 758, 725 cm−1. 1H NMR (400 MHz,
CDCl3): δ 8.68 (t, J = 9.6 Hz, 2H), 8.25−8.18 (m, 2H), 7.67−
7.55 (m, 4H), 7.47 (dd, J = 3.2, 10.0 Hz, 1H), 7.33−7.24 (m,
3H), 7.15 (d, J = 7.6 Hz, 1H), 6.39 (d, J = 10.0 Hz, 1H), 5.34
(d, J = 4.4 Hz, 1H), 3.91−3.89 (m, 1H), 2.40 (s, 3H), 1.68 (s,
1H) ppm. 13C NMR (100 MHz, CDCl3): δ 140.0, 138.4, 130.9,
130.7, 130.6, 130.0, 128.7, 128.6, 128.1, 127.3, 126.9, 126.8,
126.6, 126.4, 126.2, 124.1, 123.9, 123.8, 123.1, 67.6, 47.9, 21.6
ppm. HRMS (ESI-ion trap) m/z: [M + Na]+ calcd for
C25H20ONa, 359.1412; found, 359.1391.
(1R,2S)-2-(4-Ethylphenyl)-1,2-dihydrotriphenylen-1-ol
(5e). Prepared according to general procedure I. Colorless oil
(63 mg, 90%). Rf = 0.29 on silica gel (petroleum ether/ethyl
acetate 10:1, v/v). The ee was determined to be 87% using
HPLC analysis on a Chiralpak AD-H column (hexane/2-
propanol 90:10, 1.0 mL/min, λ = 254 nm). Retention times
were 40.1 (major) and 41.9 min (minor). [α]2D5 = +99.5 (c 1.00,
CHCl3). IR (neat): 3379 (br), 3064, 2931, 1664, 1605, 1509,
1449, 996, 758, 724 cm−1. 1H NMR (400 MHz, CDCl3): δ 8.69
(t, J = 8.4 Hz, 2H), 8.27−8.20 (m, 2H), 7.68−7.58 (m, 4H),
7.49 (dd, J = 3.2, 10.0 Hz, 1H), 7.38 (d, J = 7.6 Hz, 2H), 7.27
(d, J = 7.6 Hz, 2H), 6.41 (d, J = 9.6 Hz, 1H), 5.36 (s, 1H),
3.95−3.93 (m, 1H), 2.69 (q, J = 7.6 Hz, 2H), 1.70 (s, 1H), 1.28
(t, J = 7.6 Hz, 3H) ppm. 13C NMR (100 MHz, CDCl3): δ
143.3, 137.2, 131.1, 130.7, 130.6, 130.0, 129.1, 128.7, 128.6,
128.3, 127.2, 126.9, 126.8, 126.6, 126.3, 124.1, 123.9, 123.8,
123.1, 67.6, 47.6, 28.6, 15.7 ppm. HRMS (ESI-ion trap) m/z:
[M + Na]+ calcd for C26H22ONa, 373.1568; found, 373.1547.
1
1449, 1397, 1072, 751 cm−1. H NMR (400 MHz, CDCl3): δ
8.73 (t, J = 7.2 Hz, 2H), 8.31−8.23 (m, 2H), 7.68−7.44 (m,
9H), 7.38 (d, J = 6.4 Hz, 1H), 6.46 (d, J = 9.6 Hz, 1H), 5.41 (s,
1H), 4.01 (s, 1H), 1.68 (s, 1H) ppm. 13C NMR (100 MHz,
CDCl3): δ 140.1, 130.8, 130.7, 130.6, 129.9, 129.2, 128.8, 128.7,
128.6, 127.3, 127.2, 126.9, 126.8, 126.6, 126.4, 124.1, 123.9,
123.8, 123.1, 123.0, 67.6, 48.0 ppm. HRMS (ESI-ion trap) m/z:
[M + Na]+ calcd for C24H18ONa, 345.1255; found, 345.1242.
(1S,2R)-2-(4-Chlorophenyl)-1,2-dihydrotriphenylen-1-ol
(5b). Prepared according to general procedure I. Colorless oil
(69 mg, 97%). Rf = 0.28 on silica gel (petroleum ether/ethyl
acetate 10:1, v/v). The ee was determined to be 81% using
HPLC analysis on a Chiralpak AD-H column (hexane/2-
propanol 80:20, 1.0 mL/min, λ = 254 nm). Retention times
were 29.1 (minor) and 60.9 min (major). [α]2D5 = −103.5 (c
1.00, CHCl3). IR (neat): 3368 (br), 3064, 2923, 1660, 1490,
1
1446, 1399, 1090, 759 cm−1. H NMR (400 MHz, CDCl3): δ
ASSOCIATED CONTENT
8.74 (t, J = 7.6 Hz, 2H), 8.30−8.22 (m, 2H), 7.73−7.61 (m,
4H), 7.56 (dd, J = 3.2, 9.6 Hz, 1H), 7.43 (s, 4H), 6.38 (dd, J =
1.2, 10.0 Hz, 1H), 5.38 (s, 1H), 3.98−3.95 (m, 1H), 1.66 (s,
1H) ppm. 13C NMR (100 MHz, CDCl3): δ 138.7, 133.1, 130.7,
130.6, 130.5, 130.3, 129.6, 128.8, 128.6, 127.3, 127.0, 126.5,
126.4, 124.1, 124.0, 123.7, 123.2, 123.1, 67.5, 47.4 ppm. HRMS
(ESI-ion trap) m/z: [M + Na]+ calcd for C24H17OClNa,
379.0866; found, 379.0852.
■
S
* Supporting Information
General experimental methods; H and 13C NMR spectra of
1
compounds 2a−g, 2i−s, 3a−f, 4a−e, and 5a−e; 19F NMR
spectra of 2g; HPLC conditions and spectra of compounds 2a,
2i, 2l−p, 3e, 4e, and 5a; and X-ray structure data for compound
2m in CIF format. This material is available free of charge via
the Internet at http://pubs.acs.org.
(1S,2R)-2-(4-Methylphenyl)-1,2-dihydrotriphenylen-1-ol
(5c). Prepared according to general procedure I. Colorless oil
(65 mg, 96%). Rf = 0.26 on silica gel (petroleum ether/ethyl
acetate 10:1, v/v). The ee was determined to be 89% using
HPLC analysis on a Chiralpak AD-H column (hexane/2-
propanol 90:10, 1.0 mL/min, λ = 254 nm). Retention times
were 44.5 (minor) and 52.6 min (major). [α]2D5 = +142.5 (c
1.00, CHCl3). IR (neat): 3546, 3429 (br), 3030, 2922, 1665,
AUTHOR INFORMATION
Corresponding Author
*E-mail: yangdq@scnu.edu.cn. Phone: +86 20 39310068. Fax:
+86 20 31040403.
■
Notes
The authors declare no competing financial interest.
1
1514, 1450, 1377, 1073, 996, 758 cm−1. H NMR (400 MHz,
ACKNOWLEDGMENTS
■
CDCl3): δ 8.70 (t, J = 7.6 Hz, 2H), 8.27−8.21 (m, 2H), 7.63
(d, J = 24.0 Hz, 4H), 7.50 (d, J = 9.6 Hz, 1H), 7.36 (d, J = 6.0
Hz, 2H), 7.24 (d, J = 7.2 Hz, 2H), 6.40 (d, J = 10.0 Hz, 1H),
5.35 (s, 1H), 3.93 (s, 1H), 2.39 (s, 3H), 1.68 (s, 1H) ppm. 13C
NMR (100 MHz, CDCl3): δ 137.0, 136.9, 131.1, 130.7, 130.6,
130.0, 129.5, 129.1, 128.7, 128.6, 127.3, 126.9, 126.8, 126.6,
126.4, 124.1, 123.9, 123.1, 67.6, 47.6, 21.2 ppm. HRMS (ESI-
ion trap) m/z: [M + Na]+ calcd for C25H20ONa, 359.1412;
found, 359.1399.
(1S,2R)-2-(3-Methylphenyl)-1,2-dihydrotriphenylen-1-ol
(5d). Prepared according to general procedure I. Colorless oil
(62 mg, 92%). Rf = 0.22 on silica gel (petroleum ether/ethyl
acetate 10:1, v/v). The ee was determined to be 79% using
HPLC analysis on a Chiralpak AD-H column (hexane/2-
We gratefully thank the National Natural Science Foundation
of China (21172081 and 21372090), the Natural Science
Foundation of Guangdong Province (S2013020013091), and
the Guangzhou Pearl River New Star Plan of Science and
Technology Program (2012J2200015) for financial support as
well as the Scientific Research Foundation of the Graduate
School of South China Normal University (2012kyjj238).
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