Intramolecular Stereospecific Skeletal Rearrangement via Nonclassical Carbocations

Abstract

Abstract A stereospecific, Lewis acid-catalyzed intramolecular nucleophilic substitution at fully substituted carbon stereocenters is described, proceeding through nonclassical cyclopropyl carbinyl (CPC) carbocation intermediates and complete skeletal rearrangement. The method displays excellent regio- and diastereoselectivity, offering a general strategy for exploiting nonclassical carbocations in stereoselective synthesis.