Nucleophilic substitution reactions of trimethylsilylmethyl arenesulfonates with anilines and benzylamines in acetonitrile

Abstract

The results of kinetic studies on the reactions of trimethylsilylmethyl arenesulfonates, 1(Me3SiCH2OSO2C6H4Z), with anilines and benzylamines in acetonitrile at 65.0 °C are reported, the relatively large positive value of the cross-interaction constant between substituents in the nucleophile (X) and leaving group (Z), ρxz, indicates that the reaction proceeds by a SN2 process with a relatively tight transition state. The enhanced rate of 1 compared with the rates for other corresponding carbon analogues leads us to conclude that the destabilizing effect of the α-silyl group on the ground state of 1 due to geminal interaction is important not only for SN1 but also for SN2 reactivities.