The reduction of methyl (S)-(+)-mandelate, 1, produces the expected 2-phenylethanol, 3, and the unexpected optically pure 1-phenylethanol, 6, by a stereospecific oxygen atom metathesis; which occurs through a styrene oxide intermediate, whose concentration varies with solvent polarity.
References
1.
(a) AngelisY.S., and SmonouI.Tetrahedron Lett., 1997, 38, 8109
2.
AngelisY.S., and SmonouI.Tetrahedron Lett., 1998, 39, 2823.
3.
StephensonL.M., and MatternD. L.J. Org. Chem., 1976, 41, 3614.
4.
The absolute configuration and enantiomeric purity of 3 have been confirmed previously: (a) ElsenbaumerR.L., and MosherH. S.J. Org. Chem., 1979, 44, 600
5.
HutchinsR.O., KandasamyD., MaryanoffC. A., MasilamaniD., and MaryanoffB. E.J. Org. Chem., 1977, 42, 82
6.
DePuyC. H., BreitbeilF. W., and DeBruinK. R., J. Am. Chem. Soc., 1966, 88, 3347.
7.
HoreauA., Tetrahedron, 1975, 31, 1307.
8.
Epoxide opening occurs mainly (~90%) on the primary carbon leading to the sec-alcohol. See NystromR.F., and BrownW. G.J. Am. Chem. Soc., 1948, 70, 3738.
9.
CrosslandR.K., and ServisK. L.J. Org. Chem., 1970, 35, 3195.
