Factors Controlling the Equilibrium of Pt-Catalyzed [1,2]- versus [1,3]-Acyloxy Migration

Abstract

Pick a pathway: Upon activation with an electrophilic transition-metal catalyst, a propargylic acetate undergoes competing [1,2]- and [1,3]-acyloxy migration depending on the reaction temperature as well as the substituent pattern around the alkyne. The nature of the catalyst also affects the reaction course. The reactions provided clear evidence for the interconversion between carbenoid and allene intermediates (see scheme).