Mechanism of triflimide-catalyzed [3,3]-sigmatropic rearrangements of N-allylhydrazones—predictions and experimental validation

Abstract

Computational analysis of the triflimide catalyzed [3,3]-sigmatropic rearrangement of N-allylhydrazones, using density functional theory calculations, is reported. Key mechanistic insight was obtained and predictions derived therefrom were confirmed experimentally through temperature dependence studies. The computational results have led to the development of electron deficient N-allylhydrazones capable of reacting under mild reaction conditions. Application of the rearrangement to form a new sp³ stereogenic center is reported for the first time.