Modular Synthesis of Enantioenriched α-Chiral Homoallylic Amidines Enabled by Relay Ir/Cu Catalysis

The cascade of Ir-catalyzed enantioselective allylic amination and Cu-catalyzed alkyne-azide cycloaddition was designed for the asymmetric synthesis of homoallylic amidines. The nucleophilic addition of an in situ-generated enantioenriched tertiary allylamine to a ketenimine intermediate triggers a rapid and stereospecific zwitterionic aza-Claisen rearrangement in a 1,3 -chiral transfer manner. The approach allows modular access to enantioenriched alpha-chiral homoallylic amidines in high yields with a high level of enantiomeric purity.

Automated summary

The cascade reaction of Ir-catalyzed enantioselective allylic amination and Cu-catalyzed alkyne-azide cycloaddition allows for the efficient synthesis of enantioenriched homoallylic amidines.