Issue 1, 1989

Carbonium ion rearrangements controlled by the presence of a silyl group

Abstract

γ-Silyl tertiary alcohols rearrange in protic acid with 1,2-shift of hydride, phenyl, or alkyl groups, and loss of the silyl group to give alkenes. The placing of the silyl group thus controls the carbonium ion rearrangement in a preparatively useful way. Methoxycarbonyl groups do not migrate; instead, cyclopropanes are formed, except when the conformation suitable for cyclopropane formation is unattainable. When the alkene product is 2,2-disubstituted, it can be reprotonated under the reaction conditions and does not therefore always survive. This can be avoided by carrying out the reaction using a Lewis acid on the silyl ether. The starting γ-silyl alcohols are prepared by a variety of versatile methods.

Article information

Article type
Paper

J. Chem. Soc., Perkin Trans. 1, 1989, 115-124

Carbonium ion rearrangements controlled by the presence of a silyl group

I. Fleming, S. K. Patel and C. J. Urch, J. Chem. Soc., Perkin Trans. 1, 1989, 115 DOI: 10.1039/P19890000115

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