Axially Chiral Dibenzazepinones by a Palladium(0)-Catalyzed Atropo-enantioselective C-H Arylation

Abstract

Atropo-enantioselective C-H functionalization reactions are largely limited to the dynamic kinetic resolution of biaryl substrates through the introduction of steric bulk proximal to the axis of chirality. Reported herein is a highly atropo-enantioselective palladium(0)-catalyzed methodology that forges the axis of chirality during the C-H functionalization process, enabling the synthesis of axially chiral dibenzazepinones. Computational investigations support experimentally determined racemization barriers, while also indicating C-H functionalization proceeds by an enantio-determining CMD to yield configurationally stable eight-membered palladacycles.

Keywords: C−H activation; asymmetric catalysis; atropisomer; axial chirality; palladium.