Molecular rearrangements through thermal [1,3] carbon shifts

Abstract

Molecular rearrangements through thermal [1,3] carbon shifts, such as vinylcyclopropane-to-cyclopentene and vinylcyclobutane-to-cyclohexene isomerizations, were recognized and exemplified repeatedly from 1960–1964. Serious mechanistic studies of these and related rearrangements over the past 40 years have provided ample grounds for interpreting them as processes taking place by way of conformationally flexible but not statistically equilibrated diradical intermediates. Orbital symmetry theory fails to account for the stereochemical characteristics of [1,3] carbon shifts. For sigmatropic reactions of this class the theory can no longer be retained as a valid basis for mechanistic interpretations, or even as a serious contender for consideration as a mechanistic possibility.