Enantioselective Electrochemical C–H Activation Enabled by Sustainable 3d Transition Metal Catalysis

Enantioselective metallaelectro-catalyzed C─H activation represents an innovative strategy for enabling the transition of organic synthesis to a more resource-economic mode of operation. It circumvents substrate prefunctionalization by directly exploiting otherwise inert C─H bonds to construct complex three-dimensional scaffolds from simple molecular building blocks. Furthermore, the mild electrocatalytic conditions evade chemical oxidants, while producing molecular hydrogen as the sole by-product, enabling the connection of organic synthesis to a possible future decentralized green hydrogen economy. Still, disclosed methodologies predominantly rely on noble metal catalysts. Examples using earth-abundant 3d transition metals remain scarce despite the substantially improved ecological and economic implications and diminished toxicity. This work addresses this shortcoming by investigating the first enantioselective nickelaelectro-catalyzed C─H activation and various cobaltaelectro-catalyzed conversions. On this occasion, the synthetic versatility is examined and various mechanistic experiments are presented for fostering future developments.