LETTER
Rhenium-Catalyzed Epoxide Deoxygenation
2245
vacuum in an NMR tube. The mixture was immersed in a water–
(5) (a) Reetz, M. T.; Plachky, M. Synthesis 1976, 199.
glycol bath thermostated at 75.0 ± 0.2 °C for 100 h. The conversion
(b) Denis, J. N.; Magnane, R.; Van Eenoo, M.; Krief, A.
Nouv. J. Chim. 1979, 3, 705. (c) Caputo, R.; Mangoni, L.;
Neri, O.; Palumbo, G. Tetrahedron Lett. 1981, 22, 3551.
(d) Mangette, J. E.; Powell, D. R.; West, R. J. Chem. Soc.,
Chem. Commun. 1993, 1348. (e) Mangette, J. E.; Powell, D.
R.; Calabrese, J. C.; West, R. Organometallics 1995, 14,
4064. (f) Mangette, J. E.; Powell, D. R.; Firman, T. K.; West,
R. J. Organomet. Chem. 1996, 521, 363.
1
was measured by H NMR, via comparing integrals of alkene and
epoxide proton signals with those of the 1,4-di-tert-butylbenzene
standard and comparing the initial epoxide/di-tert-butylbenzene
ratio. Those compounds, which had not been completely converted
to alkene, were further heated to 105 ºC and periodically measured
by NMR until the reaction was complete.
Deoxygenation of 1-Dodecene Oxide
A mixture of 1-dodecene oxide (0.62 mL, 2.82 mmol), PPh (0.88
(6) (a) Calo, V.; Lopez, L.; Mincuzzi, A.; Pesce, G. Synthesis
1976, 200. (b) Ogawa, A.; Miyake, J.; Murai, S.; Sonoda, N.
Tetrahedron Lett. 1985, 26, 669. (c) Dittmer, D. C.; Zhang,
Y.; Discordia, R. P. J. Org. Chem. 1994, 59, 1004.
3
g, 3.36 mmol) and Tp¢ReO (0.080 g, 0.15 mmol) was heated to re-
3
flux in benzene (30 mL) under Ar for 86 h. [Care must be taken to
exclude atmospheric O to prevent aerobic oxidation of the catalyt-
(7) (a) Rosenblum, M.; Saidi, M. R.; Madhavarao, M.
Tetrahedron Lett. 1975, 16, 4009. (b) Alper, H.; Des
Roches, D. Tetrahedron Lett. 1977, 18, 4155. (c) Hayasi,
Y.; Schwartz, J. Inorg. Chem. 1981, 20, 3473. (d) Umbreit,
M. A.; Sharpless, K. B. Org. Synth. 1981, 60, 29. (e) Sato,
M.; Oshima, K. Chem. Lett. 1982, 157. (f) Miyata, N.;
Santa, T.; Hirobe, M. Chem. Pharm. Bull. 1984, 32, 377.
(g) Moloy, K. G. Inorg. Chem. 1988, 27, 677. (h) Sarmah,
P.; Barua, N. C. Tetrahedron Lett. 1988, 29, 5815.
2
ically active Re (V) intermediate.] Removal of solvent, followed by
chromatography on silica (eluent: hexane) gave 1-dodecene (447
mg, 2.66 mmol, 94% yield) after removal of the chromatographic
solvent in vacuo.
Deoxygenation of cis-Stilbene Oxide
A mixture of cis-stilbene oxide (1.50 g, 7.65 mmol) and PPh (2.21
3
g, 8.42 mmol) was added to Tp¢ReO (0.20 g, 0.38 mmol) in ben-
3
zene (10 mL) and heated to reflux for 24 h under Ar. Removal of
solvent, followed by chromatography on silica (eluent: hexane)
gave cis-stilbene (1.26 g, 7.00 mmol, 91.5%) after removal of sol-
vent in vacuo.
(i) Chowdhury, P. K. J. Chem. Res., Synop. 1990, 192.
(j) Whinnery, L. L. Jr.; Henling, L. M.; Bercaw, J. E. J. Am.
Chem. Soc. 1991, 113, 7575. (k) Mitchell, P. W. D. Org.
Prep. Proced., Int. 1990, 22, 534. (l) Isobe, H.; Branchaud,
B. P. Tetrahedron Lett. 1999, 40, 8747.
(
(
8) Arterburn, J. B.; Liu, M.; Perry, M. C. Helv. Chim. Acta
002, 85, 3225.
9) Gable, K. P.; Brown, E. C. J. Am. Chem. Soc. 2003, 125,
1018.
Acknowledgment
2
This work was supported by the National Science Foundation
1
(
CHE-0078505). ECB wishes to thank the OSU Department of
(
10) (a) Herrmann, W. A.; Ding, H.; Kühn, F. E.; Scherer, W.
Organometallics 1998, 17, 2751. (b) Romão, C. C.; Kühn,
F. E.; Herrmann, W. A. Chem. Rev. 1997, 97, 3197.
11) Holm, R. H.; Donahue, J. P. Polyhedron 1993, 12, 571.
12) After 4 h, a trace of alkene was observed. However, the
major product was reaction of the carbonyl oxygen to form
2-methyl-5-hydroxymethyloxazoline.
Chemistry for an N. L. Tartar Fellowship.
(
(
References
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(
1) Gable, K. P.; Brown, E. C. Organometallics 2000, 19, 944.
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1395. (b) Johnson, W. S.; Plummer, M. S.; Pulla Reddy, S.;
(13) Tp¢ReO was prepared by the method of Mayer, et al.:
3
Bartlett, W. R. J. Am. Chem. Soc. 1993, 115, 515.
3) Carbohydrates as Organic Raw Materials II; Descotes, G.,
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(a) Matano, Y.; Northcutt, T. O.; Brugman, J.; Bennett, B.
K.; Lovell, S.; Mayer, J. M. Organometallics 2000, 19,
2781. (b) In this method Re O reacted with 2 equivalents
(
(
2
7
4) (a) Wittig, G.; Haag, W. Chem. Ber. 1955, 88, 1654.
trifluoroacetic anhydride in THF, followed by addition of
KTp¢. The solid trioxo complex precipitates and is collected
by filtration and washed.
(
(
b) Vedejs, E.; Fuchs, P. L. J. Am. Chem. Soc. 1973, 95, 822.
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1
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(
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Synlett 2003, No. 14, 2243–2245 © Thieme Stuttgart · New York