R. Chen et al. / Tetrahedron 57 42001) 9837±9842
9841
are not corrected. NMR spectra were recorded as CDCl3
solutions on VXL-300 and Fx-90Q instruments H NMR
&2)-&2R,3S)-Epoxy-3-&4-methoxyphenyl)-1-phenylpropan-
20
1
1-one &2c): colorless solid, mp 60±628C; [a]589
&300 and 90 MHz) chemical shifts are reported as d values
in parts per million &ppm) relative to tetramethylsilane
&dH0.0 ppm) as internal standard. Infrared spectra were
recorded on a Perkin±Elmer 983 FT-IR spectrometer as
liquid ®lms on potassium bromide plates unless otherwise
noted. Mass spectral measurements were performed on a
Finnigan 4021 or Finningan MAT 8430 gas chromato-
graph/mass spectrometer at 70 eV and mass data were
tabulated as m/z values. Elemental analyses were carried
out on an MOD-1106 elemental analyzer. All reactions
were monitored by thin layer chromatography &TLC)
using silica gel GF254. Products were puri®ed either by
recrystallization or ¯ash column chromatography &FCC)
on silica gel manufactured in Qingdao Marine Chemical
Factory, eluting with solvent mixtures of light petroleum
&bp 60±908C) and ethyl acetate.
2256.58&c 0.66, CHCl3) &91% ee).
&2)-&2R,3S)-Epoxy-3-&4-chlorophenyl)-1-phenylpropan-1-
20
one &2d): colorless solid, mp 68±698C; [a]589 2216.98 &c
0.99, CHCl3) &94% ee).
&2)-&2R,3S)-Epoxy-3-&2-methoxyphenyl)-1-phenylpropan-
20
1-one &2e): colorless solid, mp 90±918C; [a]589 232.98
&c 1.11, CHCl3) &92% ee).
&2)-&2R,3S)-Epoxy-3-&1-naphthyl)-1-phenylpropan-1-one
20
&2f): colorless solid, mp 106±1078C; [a]589 181.38 &c
0.50, CHCl3) &84% ee).
&2)-&2R,3S)-Epoxy-3-phenyl-1-&2-methoxymethyloxy-
phenyl)propan-1-one&2g): colorless solid, mp 77±788C;
20
[a]589 2116.88&c 0.415, CHCl3) &73% ee).
Enantiomeric excess determination was performed by using
chiral phase HPLC analysis &OD column, 46 mm£250 mm,
from Daicel Chemical Industries, hexane/2-propanol, 9:1,
0.7 mL min21) based on comparison of retention times
with the racemic ones. Optical rotations were measured on
materials isolated by column chromatography using a
Perkin±Elmer polarimeter 341.
&2)-&4R,5S)-Epoxy-2-methyl-5-phenylpenta-3-one &2h):
20
colorless oil; [a]589 2103.18 &c 0.55 CHCl3) &82% ee).
1.3.2. Synthesis of Gd0O-i-Pr)3-0S)-6,60-diphenyl-BINOL
complex. &S)-6,60-diphenyl-BINOL &56 mg, 0.125 mmol)
in THF &5 mL) was added to Gd&O-i-Pr)3 &42 mg,
0.0125 mmol) in THF &5 mL) at room temperature. After
stirring at room temperature overnight, the resulting solu-
tion was dried under reduced pressure for 12 h at room
temperature. FAB &m/z): 972, 927, 855, 837, 816, 782,
744, 701, 667, 629, 607, 568, 514, 476, 454, 438, 420,
389, 362, 340, 313, 295, 267, 248, 219. IR &®lm): 3024,
1.2. Materials
All anhydrous solvents were puri®ed and dried by standard
techniques just before use. &S)-BINOL was commercial
material. Substrates of 1a±h were synthesized as described
in Refs. 4b and 7. Liangds of &S)-6,60-dibromo-BINOL and
&S)-6,60-diphenyl-BINOL were synthesized according the
procedures described in Ref. 10.
2971, 2870, 1615, 1586, 1574, 1172, 1242, 1293 cm21
.
Anal. Calcd for C, 64.42%; H, 4.14%. Found for C,
64.11%; H, 4.34%.
Acknowledgements
1.3. General procedure for the catalytic asymmetric
epoxidation with Gd0O-i-Pr)3-0S)-6,60-diphenyl-BINOL
complex
Financial supports from DSM Research, Platform Life
Sciences, the National Natural Sciences Foundation of
China and the State Key Project of Basic Research
To a suspension of MS4 A &1.0 g) in THF &10 mL) was
added &S)-6,60-diphenyl-BINOL &56 mg, 0.125 mmol) and
then Gd&O-i-Pr)3 &42 mg, 0.0125 mmol) at room tempera-
ture. After stirring at room temperature overnight, chalcone
2a &520 mg, 125 mmol) was added and the resulting mixture
was stirred for an additional 30 min at the same temperature.
To this solution was added a toluene solution of the cumene
hydroperoxide &1.05 mL, 3.75 mmol) in toluene. After stir-
ring for a certain time at room temperature, the reaction
mixture was treated with saturated NH4Cl aq. &1.5 mL)
and extracted with EtOAc &10 mL£3). The combined
organic extracts were washed with brine, dried with
Na2SO4, and concentrated, and puri®ed by ¯ash chromato-
graphy &EtOAc/hexane1:30).
&Project 973, No.
acknowledged.
G
2000048007) are gratefully
References
1. Roberts, S.; Skidmore, J. Chem. Br. 2000, 31.
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3. &a) Enders, D.; Zhu, J.; Raabe, G. Angew. Chem., Int. Ed. Engl.
1996, 35, 1725. &b) Yu, H. B.; Zheng, X. F.; Lin, Z. M.; Hu,
Q. S.; Huang, W. S.; Pu, L. J. J. Org. Chem. 1999, 64, 8149.
&c) Enders, D.; Kramps, L.; Zhu, J. Terahedron: Asymmetry
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M. J. Am. Chem. Soc. 1998, 63, 3666. &e) Watanabe, S.;
Kobayashi, Y.; Arai, H.; Bougauchi, M.; Shibasaki, M.
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Sasai, T.; Bougauchi, M.; Shibasaki, M. J. Org. Chem. 1998,
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410.
1.3.1. Compounds 2a±h. &2)-&2R,3S)-Epoxy-1,3-diphenyl-
propan-1-one &2a) in 95% ee as a colorless solid, mp
20
64±658C; [a]589 2253.78 &c 0.81, CHCl3).
&2)-&2R,3S)-Epoxy-3-&4-methylphenyl)-1-phenylpropan-1-
20
one &2b): colorless solid, mp 70±718C; [a]589 2219.98 &c
0.70, CHCl3) &93% ee).