Enantioselective Three-Component Radical Alkene Diazomethyl-Cyanation Enabled by Copper/Photoredox Dual Catalysis

Radical-mediated alkene dicarbofunctionalizations enable the construction of molecular complexity and the exploration of diverse C(sp3)-rich scaffolds. However, catalytic enantioselective three-component versions are underdeveloped. Herein, we report a copper/photoredox dual-catalyzed enantioselective alkene diazomethyl-cyanation. The key to the success is the selection of appropriate photocatalyst for the generation of diazomethyl radicals from α-iodonium diazo compounds and the introduction of a chiral bis(oxazoline) copper catalyst for the radical-metal crossover process. This protocol constitutes the asymmetric simultaneous incorporation of cyano and diazomethyl moieties across an alkene, providing general access to enantioenriched β-cyanodiazo compounds with tertiary or quaternary carbon stereogenic centers under mild conditions.