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

Central 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 alpha,beta-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.

Automated summary

The desymmetrization approach enables the construction of centrally chiral unfunctionalized arenes from unsymmetrically substituted arene rings. This approach is based on a [4+2]-cycloaddition reaction and greatly simplifies the synthesis of chiral arenes with outstanding enantioselectivities.