Nickel-electrocatalyzed enantioselective C–H activations for chemo-divergence

Abstract

Enantioselective electrocatalysis bears unique potential for the sustainable assembly of enantiomerically enriched molecules1–7. This approach allows electro-oxidative C–H activation to be performed paired to the hydrogen evolution reaction8,9. While recent progress featured scarce transition metals with limited availability10–17, we, herein, reveal that the Earth-abundant 3d transition-metal nickel is characterized by unique performance, while having high natural abundance18 and reduced toxicity19. Thereby, electrocatalytic C–H activation enabled enantioselective desymmetrizations with bicyclic alkenes, leading to three-dimensional molecular building blocks with multiple stereogenic elements20. Here, ligand optimization was guided by smart feature analysis for enantioselectivity enhancement. The detailed mechanistic investigation by experimental studies with organometallic intermediates in conjunction with computational studies identified key features of the ligand design including non-covalent interactions21,22 to guarantee full selectivity control.