Organometallic Electrochemical Synthesis (OES): Enabling C–H and C–X Bond Functionalization

Abstract

Organometallic electrochemical synthesis (OES) is a rapidly emerging synthetic domain that elegantly merges transition metal catalysis with electrochemistry, offering a powerful and sustainable complement to traditional organic synthesis. At its core, organometallic species serve as versatile molecular electrocatalysts, precisely regulating electron flow at electrode–solution interfaces and orchestrating controllable redox conversions, thereby establishing a unique mechanistic paradigm distinct from conventional organic electrochemistry, which often relies on radical pathways. Our group has long focused on OES-enabled C–H (carbon–hydrogen) and C–X (carbon–halogen) bond functionalization under this innovative theoretical framework, aiming to address long-standing challenges in synthetic efficiency, atom economy, and selectivity. A key advantage of electrochemistry is its ability to achieve precise, real-time modulation of the oxidation states of organometallic intermediates via heterogeneous interfacial electron transfer. This strategy circumvents the major drawbacks of traditional stoichiometric redox reagents, which often interact unfavorably with catalysts and generate large amounts of toxic byproducts or chemical waste. Anodic oxidation, in particular, efficiently activates inert C–H bonds under mild conditions, enabling challenging C–H bond cleavage and stereoselective carbon–carbon (C–C) and carbon–heteroatom (C–Y) framework formation, while maintaining strict control over the reductive elimination process. Through rational design and introduction of custom chiral ligands, we further manipulate stereoselectivity and achieve highly enantioselective asymmetric functionalization, a critical goal in pharmaceutical and fine chemical synthesis. On the other hand, cathodic reduction primarily facilitates the reductive cross-coupling of carbon–halogen bonds. By eliminating the need for extraneous reducing agents, this approach sustains stable catalytic performance and avoids issues related to reagent activation, deactivation, and side reactions. Chiral induction strategies, when integrated into the cathodic catalytic cycle, deliver cross-coupling products with high enantiomeric excess. Beyond single-electrode reactions, we further explore paired electrolysis and photoassisted paired electrolysis, which synergize anodic oxidation and cathodic reduction in one cell, significantly boosting electron transfer efficiency and expanding the scope of synthetically useful transformations. In this Account, we systematically summarize our recent advances covering anodic oxidation mediated C–H functionalization, cathodic reductive cross-coupling, and paired electrolysis enabled chemical transformations. Rational ligand design, electrode optimization, and detailed mechanistic studies have afforded a suite of versatile, user-friendly synthetic protocols. These strategies provide ecofriendly, scalable pathways for the construction of complex molecules and pharmaceutical intermediates, aligning with the global pursuit of green and sustainable chemistry. The unique strengths of OES, accurate redox modulation, controllable reaction selectivity, and robust functional group compatibility, establish it as a field with remarkable growth potential and bright application outlooks in contemporary organic synthesis.