Photoinduced copper-catalyzed asymmetric cyanoalkylalkynylation of alkenes, terminal alkynes, and oximes†

Abstract

The asymmetric dicarbofunctionalization of alkenes via a radical relay process can provide routes to diverse hydrocarbon derivatives. Three-component carboalkynylation, limited to particular alkyl halides and using readily available cycloketone oxime esters as redox-active precursors, is restricted by the available pool of suitable chiral ligands for broadening the redox potential window of copper complexes and simultaneously creating the enantiocontrol environment. Herein, we report a new hybrid tridentate ligand bearing a guanidine–amide–pyridine unit for photoinduced copper-catalyzed cyanoalkylalkynylation of alkenes. Leveraging the copper catalyst’s redox capability is achieved via merging the electron-rich ligand with a readily organized configuration and enhanced absorption in the visible light range, which also facilitates the enantioselectivity. The generality of the catalyst system is exemplified by the efficacy across a number of alkenes, terminal alkynes and cycloketone oxime esters, working smoothly to give alkyne-bearing nitriles with good yields and excellent enantioselectivity. A mechanistic study reveals that the chiral copper catalyst meets the requirements of possessing sufficient reduction ability, good light absorption properties, and appropriate steric hindrance.