Science of Synthesis

Xing, Y.-K.; Fang, P.; Wang, Z.-H.; Mei, T.-S., Science of Synthesis: Electrochemistry in Organic Synthesis, (2021) 1, 148.

In this chapter, we have summarized recent advances in electrochemical transition-metal-catalyzed C—H activation, including C—C, C—O, C—N, C—halogen, and C—P bond formation reactions. These methods avoid the need for stoichiometric chemical oxidants or reductants. Thus, they represent an environmentally benign tool for organic synthesis. Furthermore, compared with systems using chemical oxidants, certain reactions under electrochemical conditions have better efficiency and selectivity, especially in palladium-catalyzed C—H oxygenations and iridium-catalyzed C—H annulation with unsymmetrical alkynes. However, many challenges remain to be overcome before such methods are widely adopted in academic or industrial settings including (1) recycling of electrolytes, (2) development of enantioselective electrochemical C—H activation reactions, (3) improvement of C—H activation reaction efficiency, (4) development of new mediators, and (5) more detailed mechanistic studies by experiment and calculations. Synthetic organic electrochemistry is currently experiencing a renaissance, and the merger of electrochemistry with transition-metal-catalyzed C—H activation would offer new opportunities that conventional transition-metal catalysis may not have achieved. It is our belief that this method will continue to evolve into a widely used and accepted method for an increasing number of chemists.