A highly enantioselective three‐component hydroacyloxylation/1,4‐conjugate addition of ortho‐hydroxybenzyl alcohols, ynamides and carboxylic acids was developed under mild reaction conditions in the presence of a chiral N,N′‐dioxide/Sc(OTf)3 complex, which went through in situ generated ortho‐quinone methides with α‐acyloxyenamides, delivering a range of corresponding chiral α‐acyloxyenamides derivatives containing gem(1,1)‐diaryl skeletons in moderate to good yields with excellent ee values. The scale‐up experiment and further derivation showed the practicality of this catalytic system. In addition, a possible catalytic cycle and transition state model was proposed to elucidate the origin of the stereoselectivity based on X‐ray crystal structure of the α‐acyloxyenamide intermediate and product.

Asymmetric nucleophilic addition of 3-substituted N-Boc oxindoles to 3-bromooxindoles was designed to directly construct hetero-3,3′-bisoxindoles, with varying vicinal quaternary carbon stereocenters and N-substituents. The reaction progressed efficiently with high yields, good diastereo-and enantioselectivity (up to >99% ee) under mild reaction conditions catalyzed by chiral N,N′-dioxide/metal complexes. This methodology enabled the facile transformation of the generated hetero-3,3'-bisoxindoles into diverse hexahydropyrroloindole alkaloids with potential antiparasitic and anticancer properties.

A highly enantioselective isocyanide-based multicomponent reaction catalyzed by a chiral N,N′-dioxide/MgII complex was reported. A wide range of substrates were tolerated in this reaction, including alkyl- and aryl-substituted isocyanides with alkylidene malonates and various phenols, affording the corresponding phenoxyimidate products in good to excellent yields (up to 94% yield) with good to excellent enantioselectivities (up to 95.5:4.5 er). A catalytic cycle and transition state were proposed to rationalize the reaction process and enantiocontrol.