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.

An asymmetric formal [4 + 1] cycloaddition of N-unprotected oxindole 3-pyridinium salts and α-halo hydrazones to access chiral pyrazoline-spirooxindoles is realized by using a chiral N,N’-dioxide-Pr(OTf)3 complex as catalyst. The...