Photoredox cobalt-catalyzed asymmetric desymmetric reductive coupling of cyclobutenes with alkynes.

Abstract

Catalytic methods to couple alkynes and alkenes are highly valuable in synthetic chemistry. The cobalt-catalyzed intermolecular reductive coupling of alkenes and alkynes is particularly attractive due to the unique reactivity and cost-effectiveness of cobalt catalysts. However, the enantioselective transformations of this kind are less developed. The limited successful enantioselective examples are restricted to the use of electronically biased activated olefins as the coupling partners. Herein, we report an asymmetric desymmetric reductive coupling of electronically unbiased succinimide-containing cyclobutenes with alkynes to synthesize enantioenriched, synthetically important vinyl cyclobutanes via photoredox and cobalt dual catalysis. Excellent enantioselectivities, good diastereoselectivities and regioselectivities are obtained. Preliminary mechanistic studies suggest that Hantzsch ester is a better reducing reagent when used in combination with Et₃N. Density functional theory calculations reveal that the reaction proceeds more likely through a Co(III)-H migratory insertion mechanism.