Enantioselective C–H annulations enabled by either nickel- or cobalt-electrocatalysed C–H activation for catalyst-controlled chemodivergence
Tristan von Münchow, Neeraj Kumar Pandit, Suman Dana, Philipp Boos, Sven Erik Peters, Josselin Boucat, Yi‐Ru Liu, Alexej Scheremetjew, Lutz Ackermann
Abstract
Abstract Enantioselective electrocatalysis shows unique potential for the sustainable assembly of enantiomerically enriched molecules. This approach allows electro-oxidative C–H activation to be performed paired to the hydrogen evolution reaction. Recent progress has featured scarce transition metals with limited availability. Here we reveal that the earth-abundant 3 d transition metals nickel and cobalt exhibit distinctive performance for enantioselective electrocatalysis with chemodivergent reactivity patterns. Enantioselective desymmetrizations of strained bicyclic alkenes were achieved through C–H annulations. A data-driven optimization of chiral N , O -bidentate salicyloxazoline-type ligands was crucial for enhancing enantioselectivity in nickel electrocatalysis. Notably, in the transition state of the enantio-determining step, secondary weak attractive π – π and CH– π interactions were identified, reflecting the informed adaptations in the ligand design. Detailed mechanistic investigations by experimental and computational studies revealed for the nickel electrocatalysis a C–N bond-forming reductive elimination from nickel(III) and for the cobalt electrocatalysis a C–C bond-forming nucleophilic addition from cobalt(III) as the product-determining steps.