2-Hydroxy-2,3-dihydronaphthalene-1,4-diones (HDNDs) are ubiquitous in natural products and bioactive molecules, but the rapid asymmetric construction of such scaffolds remains a significant challenge to date. Reported herein is the rapid construction of the above key units via carbene-catalyzed benzoin reaction. The resolution technique of divergent reaction on racemic mixture (divergent RRM) was employed, affording both isomers of HDNDs in a one-step fashion. Disubstituted substrates afford products with two contiguous quaternary stereocenters. A series of highly selective transformations on the products can be realized, and mechanistic studies indicate that the benzoin reaction is much faster than the racemization process and the aldol reaction.