Dearomative Dienolate-Mediated Catalysis: A Remote Activation Strategy for Asymmetric Functionalization of Benzylic C-H Bonds of Heteroaryl Aldehydes

A dearomative remote activation strategy for the asymmetric functionalization of benzylic C-H bonds of heteroaryl aldehydes under bifunctional Bronsted base catalysis has been developed. The in situ generated o-QDMs-type dienolate intermediates were efficiently and stereoselectively trapped by nitroolefins through an asymmetric Michael/nitro-aldol cascade reaction. Using this strategy, a wide variety of synthetically significant tetrahydrodibenzothiophene and tetrahydrodibenzofuran derivatives were synthesized in good yields with high enantioselectivities.