Synthesis of chiral 2-aroyl-1-tetralols: Asymmetric transfer hydrgenation of 2-aroyl-1-tetralones via dynamic kinetic resolution

Article abstract of DOI:10.1002/cjoc.201180267

The dynamic kinetic resolution of 2-aroyl-1-tetralones was achieved via asymmetric transfer hydrogenation using (S,S)-RuCl(p-cymene)TsDPEN (TsDPEN=N-(tosyl)-1,2-diphenylethylenediamine) in formic acid/triethyl- amine (5:2, molar ratio), afforded the desired products in good yields (up to 85%) with diastereomeric ratio up to >99:1 and high enantiomeric excesses (up to >99%). The absolute configuration of major the product was confirmed by X-ray crystal structure analysis. Copyright

Full text of DOI:10.1002/cjoc.201180267

FULL PAPER
Synthesis of Chiral 2-Aroyl-1-tetralols: Asymmetric Transfer
Hydrgenation of 2-Aroyl-1-tetralones via Dynamic
Kinetic Resolution
Wu, Yun(吴云)
Geng, Zhicong(耿志聪)
Bai, Jinjin(白进进)
Zhang, Yawen*(张雅文)
Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and
Materials Science, Soochow University, Suzhou, Jiangsu 215123, China
The dynamic kinetic resolution of 2-aroyl-1-tetralones was achieved via asymmetric transfer hydrogenation us-
ing (S,S)-RuCl(p-cymene)TsDPEN (TsDPEN＝ N-(tosyl)-1,2-diphenylethylenediamine) in formic acid/triethyl-
amine (5∶ 2, molar ratio), afforded the desired products in good yields (up to 85%) with diastereomeric ratio up to
＞
99∶ 1 and high enantiomeric excesses (up to ＞ 99%). The absolute configuration of major the product was con-
firmed by X-ray crystal structure analysis.
Keywords dynamic kinetic resolution, asymmetric transfer hydrogenation, 2-aroyl-1-tetralones, enantioselectivity,
chiral
Introduction
and β-ketoamides10 using modified Noyori’s chiral
catalyst.
Dynamic kinetic resolution (DKR) has become a
powerful method to prepare enantiomerically enriched
compounds in high yields that overcomes the limitation
of classic kinetic resolution.1 Asymmetric transfer hy-
drogenation (ATH) is also proved to be a convenient
tool for developing new chrial center by reduction of
prochiral ketones or imines.
The enantiomerically pure chiral hydroxy carbonyl
compounds and their derivatives are of very high im-
portance as intermediates for the synthesis of many
natural products and drugs.11 Asymmetric catalytic aldol
reactions12 and Mukaiyama type-aldol reactions13 are
recognized as the most efficient and convenient meth-
ods to obtain the chiral β-hydroxy carbonyl compounds.
Besides, Krische and Baba groups independently re-
ported the synthesis of hydroxyl cyclic ketones by
enone-selective reduction using Co(dpm)2 (dpm ＝
dipivaloylmethane) and di-n-butyliodotin hydride
(n-Bu2SnIH) catalytic system, whose substrates were
limited to bearing both enone and formyl moieties.14,15
Herein, we report a highly regio-, enantio- and di-
astereoselective synthesis of 2-aroyl-1-tetralols from the
corresponding 2-aroyl-1-tetralones via asymmetric
catalytic transfer hydrogenation. During the reaction
cause, as one enantiomer of the substrate was reduced
preferably, the excess of the other enantiomer of the
substrate racemized rapidly, furnishing a DKR process,
which could serve as an efficient approach to the chiral
2-aroyl-1-tetralols. To the best of our knowledge, no
efficient and highly stereoselective synthesis of 2-aroyl-
1-tetralols was reported before, although there are a few
papers that are involved with the preparation of opti-
cally active 2-acetyl-1-tetralol or 2-benzoyl-1-tetralol.16
In 1999, Noyori and co-workers reported a highly
enantio- and diastereoselective preparation of 1,2-diol
by ATH of the benzil, in which the benzoin intermediate
with a chirally labile stereogenic center is converted to
one major stereoisomer, via dynamic kinetic resolution.2
Since then, increasing attention has been paid to the
DKR via ATH reaction using the classic Noyori’s chiral
catalyst [RuCl(p-cymene)]TsDPEN in the presence of
formic acid and triethylamine. For example, Lassaletta
and co-workers reported the first DKR process involv-
ing transfer hydrogenation of α-branched ketimines,3
then they extended the scope of the methodology to cy-
clic β-ketoesters,4 and cyclic α-branched ketones,5 pro-
viding the corresponding chiral products in excellent
stereoselectivities; Wills and co-workers reported trans-
fer hydrogenation of 1-aryl-substituted cyclic ketones;6
we also reported the DKR of α-sulfonylaldehydes7 and
β-keto sulfones.8 In order to improve the performance of
catalytic system, some research groups investigated the
effects of the modification of the diamine ligand by in-
troducing electron-withdrawing aryl sulfonyl groups
and some interesting results were observed. Excellent
examples include reduction of β-keto-α-amino esters9
Results and discussion
The starting materials were synthesized in moderate
*
E-mail: zhangyw@suda.edu.cn; Tel.: 0086-512-65880340; Fax: 0086-512-65880305
Received December 1, 2010; revised March 10, 2011; accepted March 18, 2011.
Chin. J. Chem. 2011, 29, 1467— 1472
© 2011 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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Wu et al.
FULL PAPER
yields by the method shown in Scheme 1.17
ginally influenced by the catalyst/substrate ratio. How-
ever, longer reaction time was necessary at lower cata-
lyst loading (Table 2, Entries 3 and 4).
Scheme 1 Synthesis of substrates
Table 2 Influence of the catalyst/substrate ratio on the DKR of
1a
Entry
S/C
20
t/h
14
12
24
24
Yielda/%
drb
eeb/% (major)
1
2
3
4
62
78
65
63
99∶1
99∶1
98∶2
98∶2
99
99
98
98
40
60
Reagents and conditions: (a) AlCl3, reflux; (b) NaH, THF, ArCOOMe,
50 ℃
80
a
b
Isolated yield. The enantiomeric excess and diastereomeric
ratio were determined by chiral HPLC analysis of the corre-
Initially, classic Noyori’s chiral catalyst [RuCl(p-
cymene)]TsDPEN was chosen as the catalyst for the
reaction in DMF, at 50 ℃, 2-benzoyl-3,4-dihydrona-
phthalen-1(2H)-one was chosen as the model substrate.
Fortunately, the reaction completed within 12 h, and the
product was obtained with 99∶1 dr and 98% ee. En-
couraged by these excellent results, we continued to
investigate the influence of solvents on the reaction
(Table 1).
sponding products on a Chiralcel OD-H column.
We decided to screen a series of substrates to evalu-
ate the scope of the reaction. The reaction was per-
formed at a scale of 0.5 mmol of substrate, using 0.0125
mmol of catalyst, in dioxane, at 50 ℃. As shown by the
results summarized in Table 3, good yield and excellent
dr and ee could be obtained with various Ar, except
when Ar is an ortho-substituted phenyl group (Table 3,
Entries 8 and 9). When Ar is a phenyl group substituted
by an electron-donating group at para- or meta-position,
the results were found slightly better than that of elec-
tron-withdrawing substituted Ar (Table 3, Entries 2, 3,
10, 11 and Entries 4—7). Moreover, when Ar is naph-
thalene-1- or 2-yl, or thiophen-2-yl, the reaction also
gave the corresponding products with good to excellent
diastereo- and enantioselectivities (Table 3, Entries
12—14).
Table 1 Influence of the solvents on the DKR of 1aa
We then examined the DKR of 1o under the same
reaction conditions (Eq. 1). The desired product was
obtained in 84% yield. However, to our disappointment,
only 72∶28 dr and 50% ee (major) were achieved.
According to the results, we deduced that the steric ef-
fects and the rigidity of the fused ring system may play
a very important role in this kind of reactions.
Entry Solvent
S/C Yieldb/%
drc
eec/% (major)
1
2
3
4
5
6
7
8
DMF
40
40
40
40
40
40
40
40
67
70
50
73
65
75
65
78
99∶1
98∶2
94∶6
95∶5
96∶4
98∶2
99∶1
99∶1
98
97
91
93
96
98
99
99
Toluene
CH3OH
DMSO
CH3CN
CHCl3
EtOAc
Dioxane
a All the reactions were processed under argon at 50 ℃ for 12 h.
b
c
Isolated yield. The enantiomeric excess and diastereomeric
ratio were determined by chiral HPLC analysis of the corre-
sponding products on a chiralcel OD-H column.
As can be seen from Table 1, various solvents have
little effect on the yield, diastereo- and enantioselectiv-
ity. Dioxane was the best solvent, and gave the product
in up to 78% yield, 99∶1 dr and 99% ee (Table 1, En-
try 8). So we chose dioxane as the solvent to investigate
the influence of the catalyst/substrate ratio on the reac-
tion. The results are listed in Table 2. The diastereo- and
enantioselectivity of the transformation was only mar-
The absolute configuration of product 2e (Table 3,
Entry 5) was confirmed to be (1S, 2S) by X-ray analysis
(Figure 1). The absolute configurations of products
2a—2d, 2f—2g and 2j—2n were assigned as (1S, 2S)
by analogy.
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Chin. J. Chem. 2011, 29, 1467—1472

Synthesis of Chiral 2-Aroyl-1-tetralols
Table 3 Results of DKR of 1a—1n at 50 ℃ in dioxane
a: Ar＝C6H5; b: Ar＝p-MeC6H4; c: Ar＝m-MeC6H4; d: Ar＝p-ClCC6H4; e: Ar＝p-BrC6H4; f: Ar＝p-IC6H4; g: Ar＝p-FC6H4; h: Ar＝o-ClC6H4; i: Ar＝
2,4-Cl2C6H3; j: Ar＝p-MeOC6H4; k: Ar＝m-MeOC6H4; l: Ar＝Naphthalen-1-yl; m: Ar＝Naphthalen-2-yl; n: Ar＝Thiophen-2-yl
Entry
Ar
Product
Yielda/%
78
drb
＞99∶1
＞99∶1
＞99∶1
99∶1
95∶5
98∶2
＞99∶1
ndc
eeb/% (major)
Abs config (major)
1
C6H5
2a
99
99
S,S
S,S
S,S
S,S
S,S
S,S
S,S
—
2
p-MeC6H4
2b
2c
85
3
m-MeC6H4
p-ClC6H4
78
99
4
2d
2e
72
93
5
p-BrC6H4
70
99
6
p-IC6H4
2f
72
＞99
7
p-FC6H4
2g
67
99
8
o-ClC6H4
2h
2i
＜5
＜5
82
ndc
ndc
＞99
99
9
2,4-Cl2C6H3
p-MeOC6H4
m-MeOC6H4
Naphthalen-1-yl
Naphthalen-2-yl
Thiophen-2-yl
ndc
—
10
11
12
13
14
2j
＞99∶1
99∶1
94∶6
99∶1
92∶8
S,S
S,S
S,S
S,S
S,S
2k
2l
80
75
＞99
2m
2n
85
99
70
99
a Isolated yield. b The enantiomeric excess and diastereomeric ratio were determined by chiral HPLC analysis of the corresponding prod-
ucts on a Chiralcel OD-H column or Chiralcel AD-H column. c Not determined.
Experimental
All manipulations were carried out under argon. The
reactions were monitored by TLC. NMR spectra were
recorded in CDCl3 on a Varian-Inova-400 or Varian
System-300 NMR spectrometer. The enantiomeric ex-
cess (ee) and diastereomeric ratio (dr) were determined
by HPLC analysis using a Chiralpak AD-H or a Chiral-
cel OD-H column with hexane-i-PrOH as the solvent.
High resolution mass spectrometry (HRMS) was deter-
mided by Micromass TOF-MS or Micromass LC-MS;
Optical rotations were measured on an Autopol IV
Figure 1 X-ray structure of the major diastereomer of 2e.
automatic polarimeter. IR spectra were recorded by
Varian 1000 FT-IR Spectrometer.
In conclusion, a convenient and highly stereoselec-
tive approach to chiral 2-aroyl-1-tetralols has been de-
veloped. The ATH of the corresponding 2-aroyl-1-
tetralone by using Noyori’s RuCl(p-cymene)TsDPEN
General procedure of asymmetric transfer hydro-
genation
A suspension of [RuCl2(p-cymene)]2 (3.83 mg,
0.00625 mmol) and (1S, 2S)-TsDPEN (4.58 mg, 0.0125
mmol) in dioxane (0.5 mL) was degassed three times,
catalyst and HCOOH-Et3N (n∶n＝5∶2) as the hydro-
gen source proceeds via DKR to selectively afford the
desired optically active 2-aroyl-1-tetralols in good
yields (up to 85%) and the reaction is highly stereose-
lective (up to＞99% ee, ＞99∶1 dr).
and then stirred at room temperature for 2 h.
HCOOH-Et3N (n∶n＝5∶2, 0.2 mL) and substrate 1
(0.5 mmol) were added. The reaction was stirred at 50
℃ until completion according to TLC detection. Water
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Wu et al.
FULL PAPER
1
(15.0 mL) was added to the reaction, the mixture was
then extracted with EtOAc (10 mL×3), dried over
anhydrous sodium sulfate and concentrated under
vacuum. After removal of the solvent, the residue was
purified by column chromatography on silica gel (eluent:
petroleum ether/AcOEt ＝20/1) to give the desired
35.092 min, t3＝40.695 min]; H NMR (CDCl3, 400
MHz) δ: 7.91 (d, J＝8.4 Hz, 2H), 7.48 (d, J＝8.3 Hz,
2H), 7.42—7.36 (m, 1H), 7.31—7.21 (m, 2H), 7.18 (d,
J＝7.1 Hz, 1H), 5.09 (s, 1H), 3.65 (dt, J＝11.8, 2.7 Hz,
1H), 3.47 (d, J＝4.2 Hz, 1H), 3.05—2.89 (m, 2H),
2.43—2.31 (m, 1H), 2.11—2.01 (m, 1H); 13C NMR
(CDCl3, 75 MHz) δ: 202.79, 140.13, 136.99, 136.13,
134.40, 130.06, 129.95, 129.39, 129.22, 128.54, 126.63,
68.62, 47.22, 28.68, 20.88; IR (KBr) v: 3453, 2933,
1
product, which was then analysed by IR, H NMR, 13C
NMR, HRMS, and HPLC spectroscopy.
[(1S,2S)-1-Hydroxy-1,2,3,4-tetrahydronaphtha-
len-2-yl](phenyl)methanone (2a) White solid, 78%
yield; m.p. 76—78 ℃; [α]2D5 －161.4 (c 1.01, acetone);
dr ＞99 ∶1, ee ＝99% [HPLC; Chiralpak OD-H,
i-PrOH-hexane (10∶90); t1＝10.949 min, t2＝11.930
－1
2875, 1668, 1584, 1486, 1455 cm . HRMS (ESI) calcd
for C17H1535ClO2Na [M ＋Na] ＋ 309.0658, found
309.0665.
(4-Bromophenyl)((1S,2S)-1-hydroxy-1,2,3,4-
tetrahydronaphthalen-2-yl)methanone (2e) White
solid, 70% yield; m.p. 144—146 ℃; [α]2D5 －159.0 (c
1.05, acetone); dr＝95∶5, ee＝99% [HPLC; Chiralpak
OD-H, i-PrOH–hexane (10∶90); t1＝12.800 min, t2＝
1
min, t3＝13.536 min]; H NMR (CDCl3, 300 MHz) δ:
7.97 (d, J＝7.4 Hz, 2H), 7.62 (t, J＝7.3 Hz, 1H), 7.51 (t,
J＝7.5 Hz, 2H), 7.43—7.35 (m, 1H), 7.31—7.15 (m,
3H), 5.11 (s, 1H), 3.76—3.62 (m, 2H), 3.08—2.87 (m,
2H), 2.48—2.30 (m, 1H), 2.14—2.01 (m, 1H); 13C
NMR (CDCl3, 101 MHz) δ: 204.35, 137.13, 136.20,
136.03, 133.73, 130.11, 129.21, 129.06, 128.55, 128.45,
126.56, 68.63, 47.00, 28.78, 21.07; IR (KBr) v: 3464,
1
13.460 min, t3＝18.164 min]; H NMR (CDCl3, 400
MHz) δ: 7.83 (d, J＝8.5 Hz, 2H), 7.65 (d, J＝8.6 Hz,
2H), 7.38 (d, J＝7.3 Hz, 1H), 7.31—7.09 (m, 3H), 5.09
(s, 1H), 3.64 (dt, J＝11.8, 2.7 Hz, 1H), 3.44 (d, J＝4.3
Hz, 1H), 3.05—2.85 (m, 2H), 2.44—2.29 (m, 1H),
2.11—1.98 (m, 1H); 13C NMR (CDCl3, 101 MHz) δ:
202.82, 136.97, 136.10, 134.81, 132.31, 130.01, 129.99,
129.16, 128.76, 128.47, 126.56, 68.56, 47.23, 28.61,
20.74; IR (KBr)－v: 3450, 2968, 2932, 2874, 1668, 1582,
－1
2938, 2873, 1681, 1＋597, 1487, 1450 cm . HRMS (EI)
calcd for [C17H16O2] 252.1150, found 252.1149.
[(1S,2S)-1-Hydroxy-1,2,3,4-tetrahydronaphtha-
len-2-yl](p-tolyl)methanone (2b) White solid, 85%
yield; m.p. 131—133 ℃; [α]2D5 －148.7 (c 1.02, ace-
tone); dr＞99∶1, ee＝99% [HPLC; Chiralpak OD-H,
i-PrOH-hexane (10∶90); t1＝11.461 min, t2＝12.104
min]; 1H NMR (CDCl3, 400 MHz) δ: 7.88 (d, J＝8.1 Hz,
2H), 7.39 (d, J＝7.1 Hz, 1H), 7.30 (d, J＝8.0 Hz, 2H),
7.28—7.20 (m, 2H), 7.18 (d, J＝7.4 Hz, 1H), 5.10 (s,
1H), 3.83 (d, J＝3.7 Hz, 1H), 3.71—3.65 (m, 1H),
3.05—2.90 (m, 2H), 2.47—2.32 (m, 4H), 2.10—2.01
(m, 1H); 13C NMR (CDCl3, 101 MHz) δ: 204.07,
144.66, 137.18, 136.19, 133.46, 130.09, 129.71, 129.16,
128.66, 128.36, 126.48, 68.66, 46.72, 28.77, 21.88,
21.20; IR (KBr) v: 3457, 2946, 2887, 1672, 1605, 1493,
1
1491, 1455 cm . HRMS (ESI) calcd for C17H1579Br-
O2Na [M＋Na]＋ 353.0153, found 353.0168.
X-ray crystal data for product 2e
Careful evaporation of a solution of 2e in EtOAc-
hexane (1∶5) gave a single crystal suitable for crystal-
lographic analysis. Selective crystal structure data: Em-
pirical formula C17H15BrO2; formula weight 331.20;
temperature 223(2) K; wavelength 0.71075 Å; crystal
system, orthorhombic; space group, P212121; unit cell
dimensions, a＝9.8770(11) Å, b＝12.0136(14) Å, c＝
12.1370(13) Å, α＝β＝γ＝90°; V＝1440.2(3) Å3; Z＝4;
－1
1450, 1397 cm . HRMS (ESI) calcd for C18H18O2Na
－1
Dc＝1.528 Mg/m3; absorption coefficient 2.852 mm ;
[M＋Na]＋ 289.1204, found 289.1208.
F(000)＝672; crystal size 0.70 mm×0.55 mm×0.40
mm. θ range, 3.15° to 27.49°; limiting indices, －12≤h
≤12, －10≤k≤15, －14≤l≤14; reflections col-
lected/unique, 8247/3131; (Rint＝0.0320). Final R indi-
ces [I＞2σ(I)], R1＝0.0258, wR2＝0.0614; R indices (all
data), R1＝0.0363, wR2＝0.0640; absolute structure pa-
rameter －0.007(9); largest diff. peak and hole 0.243
[(1S,2S)-1-Hydroxy-1,2,3,4-tetrahydronaphtha-
len-2-yl](m-tolyl)methanone (2c) Colorless oil, 78%
yield; [α]2D5 －153.7 (c 1.00, acetone); dr＞99∶1,
ee ＝99% [HPLC; Chiralpak OD-H, i-PrOH-hexane
1
(5∶95); t1＝19.732 min, t2＝23.604 min]; H NMR
(CDCl3, 400 MHz) δ: 7.82—7.72 (m, 2H), 7.46—7.35
(m, 3H), 7.31—7.15 (m, 3H), 5.10 (s, 1H), 3.74—3.65
(m, 2H), 3.06—2.89 (m, 2H), 2.48—2.31 (m, 4H),
2.12—2.01 (m, 1H); 13C NMR (CDCl3, 75 MHz) δ:
204.49, 138.84, 137.12, 136.19, 136.07, 134.42, 130.06,
129.14, 128.98, 128.82, 128.35, 126.45, 125.68, 68.59,
46.95, 28.70, 21.57, 20.93; IR (KBr) v: 3479, 2922,
－3
and －0.430 e•Å .
[(1S,2S)-1-Hydroxy-1,2,3,4-tetrahydronaphtha-
len-2-yl](4-iodophenyl)methanone (2f) Yield 72%;
m.p. 105—107 ℃; [α]2D5 －144.3 (c 1.03, acetone);
dr ＝98 ∶2, ee ＞99% [HPLC; Chiralpak OD-H,
i-PrOH-hexane (10∶90); t1＝15.454 min, t2＝24.920
min]; 1H NMR (CDCl3, 400 MHz) δ: 7.87 (d, J＝8.6 Hz,
2H), 7.67 (d, J＝8.6 Hz, 2H), 7.41—7.35 (m, 1H),
7.29—7.22 (m, 2H), 7.17 (d, J＝7.6 Hz, 1H), 5.09 (s,
1H), 3.63 (dt, J＝11.8, 2.8 Hz, 1H), 3.43 (d, J＝4.2 Hz,
1H), 3.05—2.87 (m, 2H), 2.43—2.28 (m, 1H), 2.11—
2.00 (m, 1H); 13C NMR (CDCl3, 75 MHz) δ: 203.23,
－1
1682, 1602, 1585, 1491, 1381 cm . HRMS (ESI) calcd
for C18H18O2Na [M＋Na]＋ 289.1204, found 289.1208.
(4-Chlorophenyl)((1S,2S)-1-hydroxy-1,2,3,4-
tetrahydronaphthalen-2-yl)methanone (2d) White
solid, 72% yield; m.p. 142—144 ℃; [α]2D5 －168.8 (c
1.02, acetone); dr＝99∶1, ee＝93% [HPLC; Chiralpak
OD-H, i-PrOH-hexane (5∶95); t1＝27.041 min, t2＝
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Chin. J. Chem. 2011, 29, 1467—1472

Synthesis of Chiral 2-Aroyl-1-tetralols
138.36, 136.99, 136.12, 135.36, 130.04, 129.87, 129.20,
128.52, 126.62, 101.66, 68.59, 47.19, 28.66, 20.81; －IR
min]; 1H NMR (CDCl3, 400 MHz) δ: 8.40 (d, J＝8.3 Hz,
1H), 8.01 (d, J＝8.2 Hz, 1H), 7.90 (d, J＝7.5 Hz, 1H),
7.80 (d, J＝7.1 Hz, 1H), 7.65—7.46 (m, 3H), 7.41—
7.13 (m, 4H), 5.11 (d, J＝2.0 Hz, 1H), 3.71 (dt, J＝11.8,
2.7 Hz, 1H), 3.16 (s, 1H), 3.06—2.95 (m, 1H), 2.95—
2.80 (m, 1H), 2.43—2.27 (m, 1H), 2.19—2.06 (m, 1H);
13C NMR (CDCl3, 101 MHz) δ: 207.61, 137.24, 136.31,
135.94, 134.15, 132.43, 130.52, 129.91, 129.10, 128.51,
128.32, 127.93, 126.71, 126.47, 126.42, 125.81, 124.43,
68.68, 50.60, 28.69, 19.95; IR (KBr) v: 3480, 3060,
1
(KBr) v: 3447, 2929, 2872, 1668, 1578, 1490 cm .
HRMS (ESI) calcd for C17H15IO2Na [M ＋Na] ＋
401.0014, found 401.0034.
(4-Fluorophenyl)[(1S,2S)-1-hydroxy-1,2,3,4-tetra-
hydronaphthalen-2-yl]methanone (2g) Colorless oil,
yield 67%; [α]2D5 －157.5 (c 0.57, acetone); dr＞99∶1,
ee ＝99% [HPLC; Chiralpak OD-H, i-PrOH-hexane
1
(5∶95); t1＝29.352 min, t2＝35.228 min]; H NMR
－1
(CDCl3, 400 MHz) δ: 8.04—7.97 (m, 2H), 7.42—7.36
(m, 1H), 7.31—7.13 (m, 5H), 5.09 (s, 1H), 3.66 (dt, J＝
11.9, 2.8 Hz, 1H), 3.58 (d, J＝3.8 Hz, 1H), 3.06—2.87
(m, 2H), 2.45—2.30 (m, 1H), 2.10—2.00 (m, 1H); 13C
2930, 1689, 1508, 1456 cm . HRMS (EI) calcd for
[C21H18O2]＋ 302.1307, found 302.1311.
[(1S,2S)-1-Hydroxy-1,2,3,4-tetrahydronaphtha-
len-2-yl](naphthalen-2-yl)methanone (2m)
White
1
NMR (CDCl3, 101 MHz) δ: 202.41, 166.07 (d, JCF＝
solid, 85% yield; m.p. 124—126 ℃; [α]2D5 －220.2 (c
1.01, acetone); dr＝99∶1, ee＝99% [HPLC; Chiralpak
AD-H, i-PrOH-hexane (10∶90); t1＝26.777 min, t2＝
4
256.2 Hz), 137.02, 136.11, 132.44 (d, JCF＝3.3 Hz),
3
131.19 (d, JCF＝10.0 Hz), 130.04, 129.16, 128.45,
2
1
126.55, 116.15 (d, JCF＝22.3 Hz), 68.62, 47.06, 28.65,
33.584 min t3＝45.837 min]; H NMR (CDCl3, 400
20.－91; IR (KBr) v: 3469, 2926, 1679, 1597, 1501, 145＋6
MHz) δ: 8.49 (s, 1H), 8.03 (dd, J＝8.6, 1.5 Hz, 1H),
8.00— 7.88 (m, 3H), 7.68—7.53 (m, 2H), 7.41 (d, J＝
6.7 Hz, 1H), 7.33—7.18 (m, 3H), 5.17 (s, 1H), 3.88 (dt,
J ＝11.7, 2.7 Hz, 1H), 3.70 (d, J ＝4.0 Hz, 1H),
3.10—2.96 (m, 2H), 2.53—2.39 (m, 1H), 2.19—2.10
(m, 1H); 13C NMR (CDCl3, 75 MHz) δ: 204.24, 137.19,
136.26, 135.92, 133.38, 132.68, 130.23, 130.12, 129.81,
129.24, 129.00, 128.93, 128.47, 128.00, 127.14, 126.56,
124.18, 68.78, 47.06, 28.78, 21.13; IR (KBr) v: 3456,
1
cm . HRMS (ESI) calcd for C17H15FO2Na [M＋Na]
293.0954; found 293.0973.
[(1S,2S)-1-Hydroxy-1,2,3,4-tetrahydronaphtha-
len-2-yl](4-methoxyphenyl)methanone
(2j)
Colorless oil, yield 82%; [α]2D5 －130.9 (c 1.02, ace-
tone); dr＞99∶1, ee＞99% [HPLC; Chiralpak AD-H,
1
i-PrOH-hexane (10∶90); t1＝45.293 min]; H NMR
(CDCl3, 400 MHz) δ: 7.97 (d, J＝8.3 Hz, 2H), 7.40 (d,
J＝7.0 Hz, 1H), 7.27—7.20 (m, 2H), 7.18 (d, J＝7.5 Hz,
1H), 6.98 (d, J＝8.2 Hz, 2H), 5.09 (s, 1H), 4.01 (d, J＝
2.6 Hz, 1H), 3.89 (s, 3H), 3.66 (d, J＝12.0 Hz, 1H),
3.07—2.90 (m, 2H), 2.48—2.35 (m, 1H), 2.09—2.00
(m, 1H); 13C NMR (CDCl3, 75 MHz) δ: 202.76, 163.85,
137.08, 136.06, 130.74, 129.97, 128.99, 128.67, 128.15,
126.25, 114.02, 68.54, 55.55, 46.22, 28.63, 21.11; IR
(KBr) v: 3472, 2935, 2840, 1673, 1600, 1510, 145＋7
－1
2956, 2873, 1672, 1＋626, 1493, 1454 cm . HRMS (EI)
calcd for [C21H18O2] 302.1307, found 302.1305.
[(1S,2S)-1-Hydroxy-1,2,3,4-tetrahydronaphtha-
len-2-yl](thiophen-2-yl)methanone (2n) Brown oil,
70% yield; [α]2D5 －131.6 (c 1.05, acetone); dr＝92∶8,
ee ＝99% [HPLC; Chiralpak AD-H, i-PrOH-hexane
(15∶85); t1＝16.446 min, t2＝23.168 min, t3＝24.404
min]; 1H NMR (CDCl3, 400 MHz) δ: 7.78 (d, J＝3.8 Hz,
1H), 7.71 (d, J＝4.9 Hz, 1H), 7.43—7.35 (m, 1H),
7.32—7.10 (m, 4H), 5.12 (d, J＝1.9 Hz, 1H), 3.76 (s,
1H), 3.55 (dt, J＝12.1, 2.7 Hz, 1H), 3.10—2.85 (m, 2H),
2.56—2.41 (m, 1H), 2.15—2.04 (m, 1H); 13C NMR
(CDCl3, 101 MHz) δ: 196.83, 143.11, 136.78, 136.02,
134.64, 132.56, 130.04, 129.10, 128.50, 128.36, 126.41,
68.70, 48.36, 28.62, 21.28; IR (KBr) v: 3482, 2944,
－1
cm . HRMS (ESI) calcd for C18H18O3Na [M＋Na]
305.1154, found 305.1180.
[(1S,2S)-1-Hydroxy-1,2,3,4-tetrahydronaphtha-
len-2-yl](3-methoxyphenyl)methanone (2k) Color-
less oil, yield 80%; [α]D25 －135.4 (c 1.0, acetone); dr＝
99∶1, ee＝99% [HPLC; Chiralpak AD-H, i-PrOH-
hexane (10∶90); t1＝22.550 min, t2＝25.462 min, t3＝
33.684 min]; 1H NMR (CDCl3, 400 MHz) δ: 7.57—7.46
(m, 2H), 7.44—7.35 (m, 2H), 7.30—7.20 (m, 2H),
7.20—7.11 (m, 2H), 5.10 (s, 1H), 3.87 (s, 3H), 3.68 (dt,
J ＝11.9, 2.8 Hz, 1H), 3.61 (d, J ＝3.9 Hz, 1H),
3.05—2.88 (m, 2H), 2.45—2.31 (m, 1H), 2.12—2.00
(m, 1H); 13C NMR (CDCl3, 101 MHz) δ: 203.84,
160.11, 137.40, 137.10, 136.14, 130.00, 129.88, 129.09,
128.31, 126.42, 120.92, 119.92, 112.83, 68.60, 55.54,
47.18, 28.64, 20.88; IR (KBr) v: 3482, 2938, 2836, 1581,
1488, 145＋5, 1377 cm － 1. HRMS (EI) calcd for
[C18H18O3] 282.1256, found 282.1259.
－1
2888, 1656, 1515, 1490, 1454 cm . HRMS (EI) calcd
for [C15H14O2S]＋ 258.0715, found 258.0705.
(2-Hydroxycyclohexyl)(phenyl)methanone
(2o)
White solid, 84% yield; m.p. 74—76 ℃; [α]2D5 ＋43.6
(c 1.00, acetone); dr ＝72 ∶28, ee (major) ＝50%
[HPLC; Chiralpak OD-H, i-PrOH-hexane (5∶95); t1＝
6.816 min, t2＝8.360 min, t3＝9.467 min, t4＝10.217
1
min]; H NMR (major) (CDCl3, 400 MHz) δ: 7.97 (d,
J＝7.3 Hz, 2H), 7.57 (t, J＝7.4 Hz, 1H), 7.48 (t, J＝7.7
Hz, 2H), 4.09 (td, J＝10.1, 4.2 Hz, 1H), 3.31—3.24 (m,
1H), 2.38 (s, 1H), 2.14—1.69 (m, 4H), 1.50—1.24 (m,
4H); 13C NMR (major) (CDCl3, 101 MHz) δ: 203.95,
136.73, 133.32, 128.81, 128.60, 70.94, 53.98, 33.76,
29.85, 25.69, 24.77; IR (major) (KBr) v: 3388, 2929,
[(1S,2S)-1-Hydroxy-1,2,3,4-tetrahydronaphtha-
len-2-yl](naphthalen-1-yl)methanone (2l) Brown oil,
yield 75%; [α]2D5 －99.5 (c 1.05, acetone); dr＝94∶6,
ee ＞99% [HPLC; Chiralpak AD-H, i-PrOH-hexane
(10∶90); t1＝19.106 min, t2＝23.410 min, t3＝34.918
－1
2857, 1673, 15＋97, 1446 cm ; HRMS (major) (EI) calcd
for [C13H16O2] 204.1150, found 204.1158.
Chin. J. Chem. 2011, 29, 1467—1472
© 2011 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.cjc.wiley-vch.de
1471

Wu et al.
FULL PAPER
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© 2011 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Chin. J. Chem. 2011, 29, 1467—1472