Asymmetric Epoxidation
3776±3782
obtained with a Shimadzu FTIR-8600 instrument. Optical rotations were
measured with a Jasco P-1020 polarimeter. Column chromatography was
conducted on silica gel BW-820MH, 70 ± 200 mesh ASTM, available from
Fuji Silysia Chemicals. Preparative thin-layer chromatography was per-
formed on a 0.5 mm  20 cm  20 cm Merck silica gel plate (60 F-254).
Enantiomeric excesses were determined by HPLC analysis with Shimadzu
LC-10AT-VP or by GLC analysis by using Shimadzu GC-17A or Perkin ±
Elmer Turbomas equipped with an appropriate optically active column, as
described in the footnotes of the corresponding tables. Complex 1 was
prepared to according to the reported procedure.[23] Tetrahydrofuran
(THF), diethyl ether, and benzene were dried and deoxygenated over
sodium benzophenone and distilled shortly before use. Anhydrous dioxane
was purchased from Kanto Chemical Co. Reagents and solvents were used
as received unless otherwise mentioned. Reaction temperature was
controlled by using a water-circulating bath and by attaching a infrared
filter to the light source. Equipment made with Pyrex glass were used in all
the experiments. Reactions were carried out under an atmosphere of nitrogen.
in CHCl3) for the material of 49% ee[25]); the absolute configuration was
not determined.
(3S,4S)-6-Acetamido-3,4-epoxy-2,2-dimethyl-7-nitrochromene: Colorless
oil; yield 54% (98% ee); [a]D25 19.9 (c 0.42 in CHCl3) ([a]2D5 23.2
(c 0.25 in CHCl3) for the material of >99% ee[26]).
(1S,2R)-1,2-Epoxy-1-phenylpropene: Colorless oil; yield 60% (89% ee);
[a]D25 49.2 (c 0.25 in CHCl3) ([a]2D5 28 (c 0.41 in CHCl3) for the
material of 68% ee[27]).
(1S,2S)-1,2-Epoxy-1-phenylpropene: Colorless oil; yield 26% (86% ee);
[a]D25
50.4 (c 0.42 in CHCl3) ([a]D25 47.8 (c 1.04 in CHCl3) for the
material of 95.5% ee[24]).
(1R,2R)-Stilbene oxide: Colorless oil; yield 52% (87% ee); [a]D25 180.3
(c 0.88 in CHCl3) ([a]D25 126 (c 0.88 in CHCl3) for the material of
48% ee[27]).
(1S,2R)-3,4-Dihydronaphthalene 1,2-oxide: Colorless oil; yield 59%
(84% ee); [a]D24
117.6 (c 0.40 in CHCl3) ([a]2D5
144.9 (c 0.33 in
CHCl3) for the material of 98% ee[26]).
General procedure for asymmetric epoxidation with complex 1 as the
catalyst: Complex 1 (2.0 mg, 2 mmol) and tetramethylpyrazine N,N'-dioxide
(16.8 mg, 0.10 mmol) were successively added to a solution of substrate
(0.10 mmol) in dioxane (1.0 mL). The whole mixture was stirred for the
period specified in the Tables 1, 2, 4 and 5 at room temperature under
irradiation with a halogen (100 W or 150 W) or an incandescent lamp
(60 W), and then concentrated in vacuo. The residue was purified by
chromatography over short silica gel column (hexane/AcOEt 9:1 to 3:2).
Enantiomeric excess and absolute configuration of the product were
determined as described in the footnotes of Tables 1, 2, 4 and 5.
(S)-Styrene oxide: Colorless oil; yield 30% (83% ee); [a]D28 36.9 (c
0.18 in C6H6) ([a]D18 44.5 (c 1.05, in C6H6) for the material of 95% ee[28]).
3,4-Epoxy-4-methyl-1-phenylpent-1-yne: Colorless oil; yield 42%
(82% ee); [a]D24
14.7 (c 0.17 in CHCl3); 1H NMR (CDCl3,
400 MHz): d 7.46 ± 7.44 (m 2H), 7.35 ± 7.29 (m, 3H), 3.44 (1H, s), 1.51
(3H, s), 1.40 (3H, s); IR (NaCl): nÄ 2990, 2967, 2928, 1599, 1491, 1445,
1381, 1304, 1250, 1117, 1042, 881, 791, 758, 690, 569 cm 1; MS (EI, 70 eV):
m/z (%): 172 (29) [M] , 156 (3), 143 (6), 129 (11), 114 (100), 88 (5); HRMS
(EI, 70 eV): calcd for C12H12O: 172.088; found: 172.088; the absolute
configuration was not determined.
3,4-Dihydro-1,2-dimethylnaphthalene-1,2-oxide: Colorless oil; yield 32%
(82% ee); [a]D26
144.7 (c 0.39 in CHCl3); 1H NMR (CDCl3, 400 MHz):
X-ray crystal structure determination of 1: Recrystallization of 1 from
chloroform and acetonitrile afforded single crystals 1 ´ (CH3CN) suitable
for X-ray structural analysis. All measurements were made on a Rigaku
RAXIS-RAPID imaging plate diffractometer with graphite monochro-
mated MoKa radiation. Structural analysis was performed by using the
teXsan crystallographic software package. The structure was solved by
heavy atom Patterson methods and expanded with Fourier techniques. All
non-hydrogen atoms were refined anisotropically. Hydrogen atoms were
included but not refined. Structural data and experimental detail are
summarized in Table 6. Crystallographic data (excluding structure factors)
for the structure reported in this paper have been deposited with the
Cambridge Crystallographic Data Centre as supplementary publication no.
CCDC-161815. Copies of the data can be obtained free of charge on
application to CCDC, 12 Union Road, Cambridge CB21EZ, UK (fax:
(44)1223-336-033; e-mail: deposit@ccdc.cam.ac.uk).
d 7.55 ± 7.51 (m, 1H), 7.23 ± 7.19 (m, 2H), 7.09 ± 7.05 (m, 1H), 2.90 (ddd,
J 6.4, 14.3, 14.3 Hz, 1H), 2.49 (ddd, J 1.5, 5.0, 14.3 Hz, 1H), 2.19 (ddd,
J 1.5, 6.4, 14.3 Hz, 1H), 1.86 (ddd, J 5.0, 14.3, 14.3 Hz, 1H), 1.76 (s, 3H),
1.55 (s, 3H); IR (KBr): nÄ 3429, 2928, 1728, 1383, 1277, 1076, 1040, 883,
814, 760 cm 1; MS (EI, 70 eV): m/z (%): 174 (23) [M] , 159 (18), 146 (100),
131 (42), 115 (26), 91 (23); HRMS (EI, 70 eV): calcd for C12H14O: 174.1045;
found: 174.1051; the absolute configuration was not determined.
3,4-Dihydro-2-methyl-1-methylenenaphthalene-2-ol: Colorless oil; yield
10%; 1H NMR (CDCl3, 400 MHz): d 7.61 (m, 1H), 7.21 ± 7.12 (m, 3H),
5.55 (s, 1H), 5.43 (s, 1H), 3.00 (ddd, J 5.5, 5.5, 16.5 Hz, 1H), 2.90 (ddd,
J 8.2, 8.2, 16.5 Hz, 1H), 1.97 ± 1.93 (m, 2H), 1.65 (brs, 1H), 1.40 (s, 3H);
IR (KBr): nÄ 3655, 2928, 1720, 1454, 1381, 1290, 1258, 1150, 1101, 1076,
903, 762 cm 1; MS (EI, 70 eV): m/z (%): 174 (61) [M] , 156 (91), 141 (93),
131 (87), 115 (100), 91 (50); HRMS (EI, 70 eV): calcd for C12H14O:
174.1037; found: 174.1045.
3,4-Dihydro-1,2-dimethylnaphthalene-1,2-diol: Colorless oil; yield 3%;
1H NMR (CDCl3, 400 MHz): d 7.66 (d, J 7.5 Hz, 1H), 7.24 ± 7.16 (m,
2H), 7.08 (d, J 7.5 Hz, 1H), 3.03 (ddd, J 5.3, 5.3, 17.2 Hz, 1H), 2.80 (ddd,
J 8.5, 8.5, 17.2 Hz, 1H), 2.61 (s, 1H), 2.46 (s, 1H), 2.03 ± 2.00 (m, 2H), 1.47
(s, 3H), 1.37 (s, 3H); IR (KBr): nÄ 3431, 2982, 2936, 1454, 1373, 1119, 1080,
Table 6. Crystallographic data and experimental details of the structure
determinations for complex 1 ´ (CH3CN).
formula
C62H47N4O3ClRu
Mr
1032.60
920, 764, 725 cm 1; MS (EI, 70 eV): m/z (%): 192 (9) [M] , 159 (100), 134
crystal dimensions [mm]
crystal system
space group
a []
0.20 Â 0.15 Â 0.35
orthorhombic
(16), 119 (100), 91 (50); HRMS (EI, 70 eV): calcd for C12H16O2: 192.1150;
found: 192.1148.
P212121
18.215(4)
3-Hydroxy-2,2-dimethyl-4-methylenechromane: Colorless oil; yield 54%
b []
28.994(5)
(97% ee); [a]D28
22.9 (c 0.38 in CHCl3); 1H NMR (CDCl3, 400 MHz):
c []
V [3]
9.241(2)
4880(1)
d 7.55 (d, J 7.5 Hz, 1H), 7.20 (t, J 7.5 Hz, 1H), 6.92 (t, J 7.5 Hz, 1H),
6.85 (d, J 7.5 Hz, 1H), 5.64 (s, 1H), 5.22 (s, 1H), 4.06 (d, J 7.0 Hz, 1H),
1.82 (d, J 7.0 Hz, 1H), 1.38 (s, 3H), 1.28 (s, 3H); IR (KBr): nÄ 2980, 1481,
1456, 1375, 1304, 1256, 1144, 1097, 943, 899, 756 cm 1; MS (EI, 70 eV): m/z
Z
4
3
1calcd [gcm
2qmax [8]
]
1.405
55
(%): 190 (100) [M] , 175 (15), 161 (33), 147 (83), 131 (23), 119 (30), 91 (51);
l (MoKa) []
0.71069
HRMS (EI, 70 eV): calcd for C12H14O2: 190.0994; found: 190.0992; the
absolute configuration was not determined.
scan mode
w
T [K]
183
(R,R)-1-Methyl-1,2-diphenyl oxirane: Colorless oil; yield 83% (86% ee);
measured reflections
unique reflections
observed reflections [I > 3s(I)]
12614
8976
6266
[a]D24 104.1 (c 0.53 in EtOH) ([a]D25
113.9 (c 0.9 in EtOH) for the
material of 95.5% ee[24]).
correction
m (MoKa) [cm
R values [I > 3s(I)]
refinement
residual electron density [e
Lorentz polarization
4.29
R 0.055, Rw 0.046
full-matrix least squares against F2
0.78/ 0.71
(1S,2R)-1-Phenylcyclohexene oxide: Colorless oil; yield 62% (79% ee);
[a]D25 79.7 (c 0.59 in benzene) ([a]2D5 116.7 (c 1.21 in benzene)
for the material of 98% ee[24]).
1
]
2-Methyl-1,2-epoxy-1,2,3,4-tetrahydronaphthalene: Colorless oil; yield
74% (88% ee); [a]D25 -143.1(c 0.71 in CHCl3) ([a]3D3 50.5 (c 1.02
3
]
Chem. Eur. J. 2001, 7, No. 17
ꢀ WILEY-VCH Verlag GmbH, D-69451 Weinheim, 2001
0947-6539/01/0717-3781 $ 17.50+.50/0
3781