route to enantiopure vinyloxiranes,34,41-48 which are
attractive building blocks for synthesis49,50 (especially
when applied to SN2 and SN2′ nucleophilic reactions51).
1.9 Hz, 1H), 3.80 (m, 1H), 5.05-5.18 (m, 2H), 6.90-6.70 (m, 5H);
13C NMR (CDCl3, 62.9 MHz) δ 16.9, 58.2, 64.9, 114.3, 125.5,
128.1, 128.5, 137.4, 140.9. Cis isomer: 1H NMR (CDCl3, 250
MHz) δ 1.56 (m, 3H), 3.67 (d, J ) 4.4 Hz, 1H), 4.19 (d, J ) 4.4
Hz, 1H), 4.87-5.00 (m, 2H), 6.90-7.60 (m, 5H); 13C NMR (CDCl3,
62.9 MHz) δ 19.2, 58.5, 61.1, 113.4, 126.6, 127.5, 127.7; IR (NaCl)
ν 3032-3066, 2978, 1652, 1496, 1268, 900, 878; MS (70 eV, EI)
m/z (%) 160 (39), 145 (67), 131 (100), 115 (31), 103 (100), 91 (23),
77 (50), 51 (33); HRMS found 160.0877, C11H12O (M+) 160.0888.
3-(1-Cycloh exen yl)-2-p h en yloxir a n e (10d ). Trans isomer:
1H NMR (CDCl3, 250 MHz) δ 1.2-2.1 (m, 8H), 3.29 (d, J ) 1.8
Hz, 1H), 3.86 (d, J ) 1.8 Hz, 1H), 5.91 (m, 1H), 7.1-7.4 (m, 5H);
13C NMR (CDCl3, 62.9 MHz) δ 22.2, 22.4, 22.8, 25.2, 57.7, 65.8,
125.4, 126.6, 127.4, 128.4, 133.5, 137.8. Cis isomer: 1H NMR
(CDCl3, 250 MHz) δ 1.2-2.1 (m, 8H), 3.61 (m, 1H), 4.12 (d, J )
4.2 Hz, 1H), 5.70 (m, 1H), 7.1-7.4 (m, 5H); 13C NMR (CDCl3,
62.9 MHz) δ 22.1, 22.2, 24.5, 25.3, 58.3, 61.1, 125.4, 127.3, 127.5,
127.9, 130.5, 135.3.
2-P h en yl-3-(1-p h en yleth en yl)oxir a n e (10e). Trans iso-
mer: 1H NMR (CDCl3, 250 MHz) δ 3.68 (m, 1H), 3.72 (d, J )
2.0 Hz, 1H), 5.46 (br s, 1H), 5.51 (d, J ) 1.0 Hz, 1H), 7.30-7.46
(m, 10H); 13C NMR (CDCl3, 62.9 MHz) δ 61.5, 62.5, 112.0, 125.6,
126.0, 128.1, 128.3, 128.5, 128.6, 137.0, 137.8, 143.9; MS (70 eV,
EI) m/z (%) 222 (15), 131 (37), 115 (100), 103 (36), 89 (38), 77
(26).
3-(1-Meth yleth en yl)-2-(2-n a p h th yl)oxir a n e (10f). Color-
less needles. Mp 65.5-66.5 °C. Trans isomer: 1H NMR (CDCl3,
250 MHz) δ 1.76-1.78 (m, 3H), 3.46 (d, J ) 1.7 Hz, 1H), 3.96
(d, J ) 1.7 Hz, 1H), 5.07-5.08 (m, 1H), 5.20 (s, 1H), 7.23-7.50
(m, 3H), 7.79-7.83 (m, 4H); 13C NMR (CDCl3, 62.9 MHz) δ 16.9,
58.5, 65.0, 114.4, 122.8, 124.9, 125.7, 126.0, 126.3, 127.7, 128.3,
133.2, 133.3, 134.9, 140.9; MS (70 eV, EI) m/z (%) 210 (100), 195
(43), 181 (31), 167 (62), 141 (60), 115 (43), 69 (32), 41 (23). Anal.
Calcd for C14H14O: C, 85.68; H, 6.71; O, 7.61. Found: C, 85.56;
H, 6.74; O, 7.70.
2-(4-Ch lor op h en yl)-3-(1-m et h ylet h en yl)oxir a n e (10g).
Trans isomer: 1H NMR (CDCl3, 250 MHz) δ 1.48 (br s, 1H), 3.67
(d, J ) 1.7 Hz, 1H), 3.79 (d, J ) 1.7 Hz, 1H), 4.89 (s, 1H), 4.98
(s, 1H), 7.18-7.31 (m, 4H); 13C NMR (CDCl3, 62.9 MHz) δ 16.8,
57.5, 65.0, 114.7, 126.8, 129.6, 133.9, 135.9, 140.6. Cis isomer:
1H NMR (CDCl3, 250 MHz) δ 1.72-1.75 (m, 1H), 3.32 (d, J )
4.2 Hz, 1H), 4.15 (d, J ) 4.2 Hz, 1H), 5.05-5.08 (m, 1H), 5.18
(br s, 1H), 7.18-7.31 (m, 4H); 13C NMR (CDCl3, 62.9 MHz) δ
19.2, 57.8, 61.1, 113.6, 127.9, 128.0, 133.2, 133.4, 136.8; MS (70
eV, EI) m/z (%) 194 (26), 179 (61), 165 (79), 159 (100), 144 (38),
139 (41), 130 (86), 115 (40), 89 (86), 69 (28), 63 (30), 50 (25), 41
(18); HRMS found 194.0498, C11H11ClO (M+) 194.0510.
3-(1-Meth yleth en yl)2-(2-th ien yl)oxir a n e (10h ). Trans iso-
mer: 1H NMR (CDCl3, 250 MHz) δ 1.73 (m, 3H), 3.57 (d, J )
2.0 Hz, 1H), 4.05 (d, J ) 2.0 Hz, 1H), 5.07-5.08 (m, 1H), 5.20
(s, 1H), 6.99 (dd, J ) 3.5, 5.0 Hz, 1H), 7.12 (dd, J ) 1.0, 3.5 Hz,
1H), 7.26 (dd, J ) 1.0, 5 Hz, 1H); 13C NMR (CDCl3, 62.9 MHz)
δ 16.8, 55.1, 65.5, 114.7, 125.1, 125.8, 127.1, 140.4, 141.3. Cis
isomer 1H NMR (CDCl3, 250 MHz) δ 1.64 (s, 3H), 3.69 (d, J )
4.0 Hz, 1H), 4.33 (d, J ) 4.0 Hz, 1H), 5.04 (s, 1H), 5.15 (s, 1H),
6.95 (dd, J ) 3.8, 5.0 Hz, 1H), 7.03-7.06 (m, 1H), 7.21 (dd, J )
1.3, 5.0 Hz, 1H); 13C NMR (CDCl3, 62.9 MHz) δ 19.2, 55.7, 61.7,
114.1, 125.2, 126.3, 126.8 (detected peaks).
Exp er im en ta l Section
Allyl Iod id es. Allyl iodides were prepared by standard
routes: methallyl iodide by Finkelstein halogen exchange with
NaI, 1-(iodomethyl)cyclohexene according to refs 52 and 53, and
1-iodo-2-phenylpropene according to refs 54 and 55.
Typ ica l P r oced u r e. To a solution of (2R,5R)-dimethylthio-
lane10,11 (0.25 mmol, 250 µL of a 0.2 M solution of dialkylthiolane
in t-BuOH/H2O 9/1, 1 equiv) in 250 µL of a mixture of t-BuOH/
H2O 9/1 was added allyl iodide (55 µL, 0.5 mmol, 2 equiv),
powdered NaOH (20 mg, 0.5 mmol, 2 equiv), and benzaldehyde
(26 mg, 0.25 mmol, 1 equiv). The reaction mixture was stirred
at room temperature. The reaction was judged complete by thin-
layer chromatography (TLC). TLC plates were visualized by UV
light and by treatment with a solution of 2,4-DNPH (400 mg in
100 mL of HCl, 1 N) to check the conversion of benzaldehyde,
and by a phosphomolybdic acid solution (1 g in 100 mL of
i-PrOH) to follow the oxirane formation. Water (2 mL) was
added. The aqueous phase was extracted with diethyl ether
(3 × 10 mL). The combined organic layers were washed with
brine, dried over MgSO4, and then concentrated to dryness. The
crude product was submitted to rapid column chromatography
(silica gel, 94/5/1 petroleum ether/diethyl ether/triethylamine)
to give the oxirane as an oil.
3-Eth en yl-2-p h en yl-oxir a n e (10a ). Spectra were identical
to those in ref 34.
2-P h en yl-3-(2-ph en yleth en yl)oxir an e (10b). Colorless crys-
tals. Mp 75 °C. Trans isomer: 1H NMR (CDCl3, 250 MHz) δ 3.48
(dd, J ) 1.9, 7.7 Hz, 1H), 3.85 (d, J ) 1.9 Hz, 1H), 6.04 (dd, J )
7.7, 16.0 Hz, 1H), 6.77 (d, J ) 16.0 Hz, 1H), 7.17-7.38 (m, 10H);
13C NMR (CDCl3, 62.9 MHz) δ 60.5, 62.9, 125.4, 126.2, 126.4,
128.0, 128.1, 128.4, 128.6, 134.2, 135.9, 137.0. Cis isomer: 1H
NMR (CDCl3, 250 MHz) δ 3.79 (dd, J ) 4.2, 8.7 Hz, 1H), 4.28
(d, J ) 4.2 Hz, 1H), 5.72 (dd, J ) 8.7 Hz, 15.9 Hz, 1H), 6.81 (d,
J ) 15.9 Hz, 1H), 7.17-7.38 (m, 10H); 13C NMR (CDCl3, 62.9
MHz) δ 59.3, 59.9, 123.0, 126.2, 126.4, 127.7, 128.2, 128.4, 128.6,
134.3, 135.2, 136.8; IR (KBr) ν 3856, 3652, 3632, 3422, 3058,
3030, 2972, 1492, 1452, 974, 890, 834, 754, 694, 550 cm-1; MS
(70 eV, EI) m/z (%) 222 (9) [M+], 206 (8), 193 (65), 189 (100),
114 (43), 77 (30), 51 (31).
(2S,3S)-3-(1-Meth yleth en yl)-2-ph en yloxir an e (10c).56 Trans
isomer: 1H NMR (CDCl3, 250 MHz) δ 1.75 (m, 3H), 3.37 (d, J )
(40) Solladie´-Cavallo, A.; Boue´rat, L.; Roje, M. Tetrahedron Lett.
2000, 41, 7309-7312.
(41) Elliott, M. C. J . Chem. Soc., Perkin Trans. 1 2000, 1291-1318.
(42) Tokunaga, M.; Larrow, J . F.; Kakiuchi, F.; J acobsen, E. N.
Science 1997, 277, 936-938.
(43) Mikame, D.; Hamada, T.; Katsuki, T. Synlett 1995, 827-828.
(44) Frohn, M.; Dalkiewicz, M.; Tu, Y.; Wang, Z.-X.; Shi, Y. J . Org.
Chem. 1998, 63, 2948-2953.
(45) Frohn, M.; Shi, Y. Synthesis 2000, 1979-2000.
(46) Zhang, W.; Lee, N. H.; J acobsen, E. J . Am. Chem. Soc. 1994,
116, 425-426.
(47) Bandini, M.; Cozzi, P. G.; Melchiorre, P.; Morganti, S.; Umani-
Ronchi, A. Org. Lett. 2001, 3, 1153-1155.
(48) Hu, S.; J ayaraman, S.; Oehlschlager, A. C. J . Org. Chem. 1996,
61, 7513-7520.
(49) Hudlicky, T.; Reed, J . W. Comprehensive Organic Synthesis;
Trost, B. M., Fleming, I., Winterfeldt, E., Eds.; Pergamon Press:
Oxford, UK, 1991; Vol. 5, pp 899-970.
Ack n ow led gm en t. We thank the PunchOrga net-
work (Poˆle Universitaire Normand de Chimie Orga-
nique), the Ministe`re de la Recherche, CNRS, the Re´gion
Basse-Normandie, and the European Union (Fonds
FEDER) for their support, and Dr. Catherine Leriverend
for her preliminary study.
(50) Erden, I. Comprehensive Heterocyclic Chemistry II; Katritzky,
A. R., Rees, C. W., Scriven, E. F. V., Padwa, A., Eds.; Pergamon:
Oxford, UK, 1996; Vol. 1A, pp 97-171.
(51) Marshall, J . A. Chem. Rev. 1989, 89, 1503-1511.
(52) Dreiding, A. S.; Hartman, J . H. J . Chem. Soc. 1953, 75, 939-
943.
(53) Kanai, T.; Irifune, S.; Ishii, Y.; Ogawa, M. Synthesis 1989, 283-
Su p p or tin g In for m a tion Ava ila ble: Enantioselective
HPLC chromatograms of the isomers of 3-ethenyl-2-phenyl-
oxirane and 3-(methylethenyl)-2-phenyloxirane. This material
286.
(54) Rigby, J . H.; Cuisiat, S. V. J . Org. Chem. 1993, 58, 6286-6291.
(55) Duboudin, J .-G.; J ousseaume, B. Synth. Commun. 1979, 9, 53-
56.
(56) Harada, T.; Akiba, E.; Oku, A. J . Am. Chem. Soc. 1983, 105,
2771-2776.
J O026085Z
9086 J . Org. Chem., Vol. 67, No. 25, 2002