Carbonium ion rearrangements controlled by the presence of a silyl group

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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.

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