Harnessing Radical Chemistry via Electrochemical Transition Metal Catalysis

Abstract

Summary The merger of transition metal catalysis and electroorganic synthesis has recently emerged as a versatile platform for the development of highly enabling radical reactions in a sustainable fashion. Electrochemistry provides access to highly reactive radical species under extremely mild reaction conditions from abundant native functionalities. Transition metal catalysts can be used as redox-active electrocatalysts to shuttle electrons, chiral information to organic substrates, and the reactive intermediates in the electrolytic systems. The combination of these strategies in this mechanistic paradigm thus makes the generation and utilization of radical species in a chemoselective manner and allows further application to more synthetically attractive enantioselective radical transformations. This perspective discusses key advances over the past few years in the field of electrochemical transition metal catalysis and demonstrates how the unique features of this strategy permit challenging or previously elusive transformations via radical pathways to be successfully achieved.

Recent Applications of Homogeneous Catalysis in Electrochemical Organic Synthesis

“…However, despite substantial growth in electrochemical synthesis, there have been only a few reports of electrochemical asymmetric catalysis. [120][121][122][123][124][125][126] In addition to the usual challenges posed by homogeneous catalysis, asymmetric electrochemical catalysis presents several additional difficulties. In particular, because phosphines can readily undergo single-electron oxidation, the chiral phosphine ligands that have been developed for transition-metal catalysis need extra precautions during reaction design.…”

Reaching the Full Potential of Electroorganic Synthesis by Paired Electrolysis

“…The synergetic application of transition metal catalysis and electrochemistry has recently emerged as a powerful synthetic strategy for the development of radical‐based transformations [33] . In the context of paired electrolysis, Chen and co‐workers recently reported a Mn‐catalyzed paired electrochemical oxychlorination of styrenes 43 for the synthesis of chloroacetophenones 44 (Figure 16A) [34] .…”

Nickel-catalyzed oxidative fluoroalkylation of aryl halides via paired electrolysis

“…Electrochemically initiated radical cross-coupling has drawn much attention for the redox-e ciency, innate scalability and compatibility of electrolytic process. 17 The combination of uorination and electrochemistry opens a new arena for the development of organo uorine methodology 18 . Recently, various electrochemically mediated approaches for uoroalkylation of organic molecules through radical addition pathway have been reported.…”