Desymmetrization of 2‐cyano‐N‐tosylbenzylidenimine with thiols and organocatalytic heterocyclization by dynamic resolution: mechanism investigation

Integrated experimental and computational approach provides a rationale for the mode of action of cinchonabased alkaloids as chiral receptors in the observed dynamic chiral resolution of the titled tandem reaction. In particular, a mechanism based on a dynamic kinetic asymmetric transformation has been unravelled in detail. Furthermore, the crucial role of “distal” H-bonding donor functionality in directing the enantioselectivity reversal of homochiral cinchona-based catalysts has been convincingly explained. The access to enantiopure tertiary isoindolinone N,S-acetals has been achieved for the first time