Chiral Primary Amine Catalyzed α‐Arylation of Simple Ketones via Asymmetric Retro‐Claisen Cleavage

Highly enantioselective α‐arylation of simple ketones has been achieved by chiral primary amine catalyzed asymmetric retro‐Claisen cleavage of β‐diketones. This mild organocatalytic strategy enables the construction of α‐aryl tertiary carbon stereocenters in good yields and excellent enantioselectivities (up to 98 % ee) with the para‐quinone monoimines as aryl sources. Furthermore, oxidative catalytic asymmetric α‐arylation has also been realized with free p‐aminophenols. C−C cleavage to arylation. Enantioselective α‐arylation of simple aliphatic ketones has been achieved via chiral primary amine catalyzed asymmetric retro‐Claisen cleavage involving β‐diketones and para‐quinone monoimines that facilitates the construction of α‐aryl tertiary carbon stereocenters in good yields and high enantioselectivities.