Recent Advances in Asymmetric [1,2]-Stevens-Type Rearrangement via Metal Carbenes

Abstract The [1,2]-Stevens rearrangement is a widely used transformation in synthetic organic chemistry. However, enantioselective versions are relatively limited and most of them rely on substrate-induced methodologies. In recent years, metal carbene chemistry has been extensively investigated, and the related asymmetric [1,2]-Stevens rearrangement has experienced rapid development by employing ylide intermediates generated from the reaction of metal carbenes with heteroatoms. This review summarizes recent advances in the asymmetric [1,2]-Stevens-type rearrangement via metal carbenes by presenting their product diversity, selectivity, and mechanistic rationale, which is organized based on the mode of chirality control. 1 Introduction 2 Substrate-Induced Asymmetric [1,2]-Stevens-Type Rearrangement 3 Catalyst-Controlled Asymmetric [1,2]-Stevens-Type Rearrangement 4 Conclusion and Outlook