Mechanism of the α-silylcarbinol to silyl ether rearrangement

Abstract

The rates of rearrangement of a wide variety of α-silylcarbinols have been measured. Hammett plots of log k vs. σ have been made for several systems, and values for ρ, for the energy of activation, and for the entropy of activation have been obtained. A mechanism which is consistent with the above data, and which involves a cyclic three-membered transition state, has been proposed for the α-silylcarbinol to silyl ether rearrangement.