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), ρ_xz, indicates that the reaction proceeds by a S_N2 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 S_N1 but also for S_N2 reactivities.