Asymmetric Synthesis of Chiral Aliphatic α‐Tertiary Aminonitriles via Organocatalytic Isomerization of Cyanoketimines

Comprehensive Summary Chiral α ‐tertiary aminonitriles are valuable synthetic intermediates. They are also found in various structures of biologically active molecules. Therefore, numerous reports of catalytic asymmetric synthesis of chiral α ‐aminonitriles continuously emerged during the past few decades. Great strides have been made for the synthesis of chiral α ‐aryl and α ‐branched alkyl aminonitriles. However, efficient methods for catalytic asymmetric synthesis of chiral α ‐linear alkyl aminonitriles remain limited. We herein report a new synthetic approach to chiral α ‐tertiary alkyl aminonitriles via catalytic asymmetric isomerization of cyanoketimines. The synthetic value of this method was illustrated by application to a concise catalytic asymmetric synthesis of vildagliptin.