Solvolytic elimination of a ?-silyl group from 1-(trifluoromethyl)-3-(trimethylsilyl)cyclobutyl tosylate provides a facile route to trifluoromethylbicyclobutane. Similarly, the straight-chain system 1,1,1-trifluoro-3-(trimethylsilyl)-2-butyl triflate yields 1-methyl-1-(trifluoromethyl)cyclopropane. The scope of the reaction is explored for numerous cyclic and acyclic ?-silyl systems containing a-perfluoroalkyl groups with the goal of developing a general methodology to prepare trifluoromethyl-substituted cyclopropanes or cyclopropyl-containing polycyclic systems. The proposed mechanism (Figure 1) in which the perfluoroalkyl group significantly enhances ?-silyl 'percaudal' participation is consistent with rate-constant and kinetic isotope effect data. 

Electron-deficient cation directed γ-silyl elimination as a tool for forming trifluoromethylcyclopropanes

242nd National Meeting (2011)

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