Catalytic Asymmetric Azidative Functionalization of Alkenes

Abstract Aliphatic azides are an important class of nitrogen‐containing compounds found in numerous biologically active molecules. Besides, they also serve as useful building blocks owning to their remarkable reactivities. Catalytic azidation of alkenes is an efficient way to produce aliphatic azides. In this respect, azidated chiral molecules can be formed if a chiral catalyst is used. The last quarter of century has witnessed a burgeoning of new methods for catalytic enantioselective azidative functionalization of alkenes to yield chiral alkyl azides. In this review, we provide a summary of the development of the asymmetric azidation of alkenes systematically, from the view of reaction models (conjugate addition, π activation, reductive elimination, and radical addition and atom transfer) combining the roles that azido sources play (nucleophilic, electrophilic, and radical). This review will be useful to the fields of azide chemistry and asymmetric alkene functionalization.