Enantioselective Synthesis of 2‐Substituted 2‐Hydroxymethylaziridines by Copper‐Catalyzed Sulfonylative Desymmetrization of 2‐Amino‐1,3‐Diols

Abstract An enantioselective protocol for the synthesis of 2‐hydroxymethylaziridines with a tetrasubstituted carbon stereocenter have been established through the copper‐catalyzed asymmetric desymmetrization of 2‐substituted 2‐amino‐1,3‐diol derivatives by monosulfonylation. The present transformation consists of a reaction sequence involving the enantioselective monosulfonylation of 2‐amino‐1,3‐diols and the intramolecular ring closure of the resultant monosulfonylated products, which provides an efficient and straightforward entry to optically active 2‐substituted 2‐hydroxymethylaziridines. The potential synthetic utility of the present reaction is exemplified by the derivatization of the obtained aziridines into a variety of nitrogen‐containing molecules such as amino alcohols and functionalized aziridine derivatives with high enantiopurities.