Copper-Catalyzed Asymmetric Vinylation of α-Cyano Substituted Carbonyl Compounds.

Based on (S)-azetidine-2-carboxylic acid-derived amides, a class of effective ligands has been developed for the Cu-catalyzed enantioselective coupling of vinyl iodides with α-cyano carbonyl compounds, including α-alkyl-substituted cyanoacetates, α-cyano lactams, and α-cyano lactones. This asymmetric transformation affords α-vinyl-α-alkyl cyanoacetates, α-vinyl-α-cyano lactams, and α-vinyl-α-cyano lactones in good to excellent enantioselectivities (up to 99% ee). A wide range of functionalized vinyl groups can be introduced at the quaternary center across these three types of substrates. Furthermore, the reaction accommodates both simple and functionalized alkyl substituents in the α-alkyl-substituted cyanoacetates. These advantages make the current coupling strategy highly valuable for constructing enantioenriched molecules featuring an all-carbon quaternary center bearing versatile and easily modifiable functional groups.