Catalytic Enantioselective de novo Construction of Chiral Arenes through Desymmetrizing Oxidative [4+2]‐Cycloaddition

Abstract

AbstractCentral chirality in arene derivatives arising out of unsymmetrically substituted arene ring is a fascinating yet rarely explored research topic. Here, we report a desymmetrization approach to centrally chiral unfunctionalized arenes, which is enabled by the enantioselective de novo construction of the arene ring. This operationally simple protocol is based on a [4+2]‐cycloaddition between polycyclic meso‐cyclohexenediones and α,β‐unsaturated aldehydes, and doesn't usually require any external oxidant. Catalyzed by a diphenylprolinol silyl ether, this reaction proceeds via dienamine intermediate and greatly simplifies the access to diversely substituted chiral arenes with outstanding enantioselectivities.