Isomer selectivity in stereocontrolled Payne rearrangement–epoxide cleavage of 2,3-epoxy alcohols in aprotic solvents: application to an enantioselective total synthesis of (+)-exo-brevicomin

Abstract

Organo-copper and -cuprate reagents may be used to trap the more reactive epoxy alkoxide isomer in a Lewis acid-catalysed Payne rearrangement process. This methodology has been used as the key step in a five-step enantioselective total synthesis of (+)-exo-brevicomin, an aggregation pheromone of the Western Pine beetle Dendroctonius brevicomis.