LETTER
Preparation of Enantiomerically Pure 3,4-Epoxy-1-butene
1617
The distilled material was dried with Na2SO4, filtered and re-dis-
tilled at atmospheric pressure to further purify the product. The
H2O/S-2 azeotrope (36.3 g) was collected as a forerun at 50–62 °C,
and S-2 (126.5 g, 67%) was collected at 63 °C. Chiral GC analysis
indicated >99% chemical purity and 99.4% ee. 1H NMR (CDCl3):
d = 5.522 (1 H, m), 5.298 (2 H, m), 3.345 [1 H, m (5), J = 3.15 Hz],
2.967 (1 H, t, J = 4.43 Hz), 2.657 (1 H, dd, J = 2.31, 5.17 Hz).
Chiral GC [30 m × 0.25 mm Cyclosil-B (J & W Scientific), 0.25 mm
film thickness, 40 °C, 7 min; 40–120 °C, 70 °C/min; 120 °C, 12
min, 8.0 psi, 7 min; 8.0–13.0 psi, 80 psi/min; 13.0 psi, 7.72 min]:
tR(S-2) 6.37 min, tR(R-2) 6.67 min. [a]D25 +9.6 (c 6.33, i-PrOH). The
literature value for S-2 is [a]D25 +8.3 (c 6.96, i-PrOH).8b
7 min, 40–120 °C, 70 °C/min, 120 °C, 12 min; 8 psi, 7 min, 8–80
psi, 13 psi/min, 80 psi, 7.72 min]: tR 14.28 min (S-1), tR 14.36 min
(R-1). [a]D20 –44.4 (c 3.02, i-PrOH).
References
(1) (a) Kozikowski, A. P.; Ghosh, A. K. J. Am. Chem. Soc. 1982,
104, 5788. (b) Kozikowski, A. P.; Ghosh, A. K. J. Org.
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(2) Walkup, R. D.; Cunningham, R. T. Tetrahedron Lett. 1987,
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(3) (a) Rama Rao, A. V.; Reddy, E. R.; Joshi, B. V.; Yadav, J. S.
Tetrahedron Lett. 1987, 28, 6497. (b) Rama Rao, A. V.;
Bose, D. S.; Gurjar, M. K.; Ravindranathan, T. Tetrahedron
1989, 45, 7031.
(4) Gurjar, M. K.; Devi, N. R. Tetrahedron: Asymmetry 1994, 5,
755.
(S)-Vinyl Ethylene Carbonate (S-5)
(S)-2-Hydroxy-3-butenyl tosylate (R-3, >99% ee, 241 g, 1.04 mol),
DMSO (166 mL), and KHCO3 (208 g, 2.08 mol, 2.0 equiv) were
charged to a 500-mL flask. The solution was heated to 60 °C over-
night to completely consume 3 according to TLC analysis. The mix-
ture was cooled to ambient temperature and poured into 1040 mL of
EtOAc. The EtOAc solution was washed with four 420-mL portions
of H2O, and the combined aqueous washes were back-extracted
with two 625-mL portions of EtOAc. The combined organic solu-
tion was washed once more with H2O, dried with MgSO4, and con-
centrated. The residue was distilled at 13 mm Hg and the material
collected at 114 °C. This afforded 84.0 g (74%) of S-5 with 99.4%
chemical purity (GC) and 99.4% ee (chiral GC). 1H NMR (CDCl3):
d = 5.917 (1 H, ddd, J = 7.00, 10.38, 17.21 Hz), 5.526 (1 H, d,
J = 17.02 Hz), 5.459 (1 H, d, J = 10.37 Hz), 5.141 (1 H, q, J = 7.28
Hz), 4.614 (1 H, t, J = 8.37 Hz), 4.171 (1 H, t, J = 7.84 Hz). Chiral
GC [30 m × 0.25 mm Cyclosil-B (J & W Scientific), 0.25 mm film
thickness, 120 °C isothermal]: tR 15.26 min (R-5), tR 15.85 min (S-
5). [a]D22 –26.1 (c 1.15, MeOH).
(5) Bergmeier, S. C.; Stanchina, D. M. J. Org. Chem. 1999, 64,
2852.
(6) Maeda, M.; Okazaki, F.; Murayama, M.; Tachibana, Y.;
Aoyagi, Y.; Ohta, A. Chem. Pharm. Bull. 1997, 45, 962.
(7) Ohgiya, T.; Nishiyama, S. Heterocycles 2004, 63, 2349.
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(9) (a) Jung, M. E.; Shaw, T. J. J. Am. Chem. Soc. 1980, 102,
6304. (b) Marco, J. L.; Rodriguez, B. Tetrahedron Lett.
1988, 29, 1997. (c) Takano, S.; Numata, H.; Ogasawara, K.
Heterocycles 1982, 19, 327. (d) Hubschwerlen, C. Synthesis
1986, 962.
(10) Howes, D. A.; Brookes, M. H.; Coates, D.; Golding, B. T.;
Hudson, A. T. J. Chem. Res., Synop. 1983, 9; J. Chem. Res.,
Miniprint 1983, 217.
(11) (a) Tokunaga, M.; Larrow, J. F.; Kakiuchi, F.; Jacobsen, E.
N. Science 1997, 277, 936. (b) Schaus, S. E.; Brandes, B.
D.; Larrow, J. F.; Tokunaga, M.; Hansen, K. B.; Gould, A.
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(12) (a) Trost, B. M.; McEachern, E. J. J. Am. Chem. Soc. 1999,
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1994, 5, 153.
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1981, 793. (b) Myers, A. G.; Widdowson, K. L. Tetrahedron
Lett. 1988, 29, 6389.
(S)-3-Butene-1,2-diol (S-1)
(S)-Vinyl ethylene carbonate (S-5, 79.0 g, 0.69 mol) was charged to
a 1-L flask and cooled in an ice bath. A solution of potassium hy-
droxide (45.0 g, 0.80 mol, 1.15 equiv) in 45 mL of H2O was added
dropwise over 35 min. The ice bath was removed and the mixture
was heated to 60 °C for 2 h. After cooling to ambient temperature,
i-PrOH (370 mL) was added and the mixture was stirred for 20 min.
The inorganic salt precipitate was removed by filtration and the sol-
ids were washed with 50 mL of i-PrOH. The combined organic so-
lution was concentrated and the residue was distilled at 10 mm Hg
with material collected at 80 °C. This afforded 50.4 g (83% yield)
of S-1 with >98% chemical purity (GC) and 99.5% ee (chiral GC).
1H NMR (CDCl3): d = 5.842 (1 H, ddd, J = 5.52, 10.51, 16.89 Hz),
5.350 (1 H, dd, J = 1.67, 17.08 Hz), 5.222 (1 H, dd, J = 1.07, 10.38
Hz), 4.250 (1 H, m), 3.670 (1 H, dd, J = 3.34, 11.26 Hz), 3.493
(1 H, dd, J = 7.42, 11.26 Hz), 2.572 (2 H, br s). MS (EI): m/z = 70
[M+ – H2O], 57 [M+ – CH2OH]. Chiral GC [30 m × 0.25 mm
Cyclosil-B (J & W Scientific), 0.25 mm film thickness, 40 °C,
(17) Boaz, N. W. US Patent No. 5312950, 1994.
Synlett 2005, No. 10, 1615–1617 © Thieme Stuttgart · New York