Application of Regio‐ and Stereoselective Functional Group Transformations of Chiral Aziridine‐2‐carboxylates

Chiral aziridine‐2‐carboxylates have two important functional groups, the carboxylate group and aziridine ring, that are useful for synthetic purposes. As both (2 R )‐ and (2 S )‐aziridine‐2‐carboxylates were commercialized in optically pure forms, we have studied to extend their synthetic utilities for the construction of various nitrogen‐containing molecules. The C2 ester group can be transformed into aldehydes, alcohols, amides, ketones, β‐ketoesters, and amines bearing diverse substituents with defined stereochemistry in high yields. In particular, ring‐opening reactions of aziridines are carried out in regio‐ and stereoselective manners toward α‐ or β‐amino cyclic and acyclic compounds in optically pure forms. The highlight of this chemistry based on the regio‐ and stereoselective functional‐group transformations of aziridine‐2‐carboxylates is exemplified by efficient and highly stereoselective syntheses of many biologically important amines, including natural products.