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. 2009 Apr 29;131(16):5763-5.
doi: 10.1021/ja901283q.

A method for the preparation of differentiated trans-1,2-diol derivatives with enantio- and diastereocontrol

Sang Min Lim  1 , Nicholas Hill, Andrew G Myers
Affiliations

A method for the preparation of differentiated trans-1,2-diol derivatives with enantio- and diastereocontrol

Sang Min Lim et al. J Am Chem Soc. .

Abstract

We describe a synthetic sequence that allows for the preparation of optically active trans-1,2-diol monosilyl ether derivatives from ketones, providing a new means for retrosynthetic simplification of differentiated diol and polyol targets. The sequence involves silyl enol ether formation, Shi asymmetric epoxidation, and then regio- and stereospecific addition of hydride, methide, or higher alkylide. The tactical combination presented has not been integrated in synthetic problem solving, so far as we are aware, but has promise for broad application.

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Figures

Figure 1
Figure 1
Reduction of the cis-tert-butyldiphenylsilyloxy epoxide 4 with BD3-THF provides evidence for a short-lived carbocationic intermediate. The data suggest that the rate of deuteride transfer is slightly more rapid than rotation about the internal C-C bond.
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