The cyclopropylcarbinyl route to γ-silyl carbocations.

ABSTRACT: The mesylate derivative of cis-1-hydroxymethyl-2-trimethylsilylcyclopropane has been prepared, along with a number of related mesylates and triflates with substituents on the 1-position. These substrates all solvolyze in CD₃CO₂D to give products derived from cyclopropylcarbinyl cations that undergo further rearrangement to give 3-trimethylsilylcyclobutyl cations. These 3-trimethylsilylcyclobutyl cations are stabilized by a long-range rear lobe interaction with the γ-trimethylsilyl group. When the substituent is electron-withdrawing (CF₃, CN, or CO₂CH₃), significant amounts of bicyclobutane products are formed. The bicyclobutanes are a result of γ-trimethylsilyl elimination from the cationic intermediate that has an unusually lon

SUBMITTER: Creary X 

PROVIDER: S-EPMC6664402 | biostudies-literature | 2019

REPOSITORIES: biostudies-literature