Recent advances in catalytic asymmetric aza-Cope rearrangement.

Aza-Cope rearrangement, as one of the fundamental reactions for C-C and C-N bond formation, has been extensively utilized for the rapid construction of synthetically challenging organic molecules. Despite significant achievements having been made in the past 80 years, catalytic enantioselective versions still remain a challenge, mainly due to the inherent nature of the reversibility of aza-Cope rearrangement. Recently, owing to the intensive development of asymmetric catalysis strategies, various chiral organocatalysts and transition-metal catalysts have been successfully applied to control the stereoselectivity of aza-Cope rearrangement, and remarkable advances have been achieved. This review highlights recent progress relating to catalytic asymmetric aza-Cope rearrangement and covers important features of these studies, including catalytic system design, mechanistic insights, stereochemistry analysis, and synthetic applications.