Transition Metal‐Catalyzed C−H Functionalization Through Electrocatalysis

Abstract

Electrochemically promoted transition metal‐catalyzed C−H functionalization has emerged as a promising area of research over the last few decades. However, development in this field is still at an early stage compared to traditional functionalization reactions using chemical‐based oxidizing agents. Recent reports have shown increased attention on electrochemically promoted metal‐catalyzed C−H functionalization. From the standpoint of sustainability, environmental friendliness, and cost effectiveness, electrochemically promoted oxidation of a metal catalyst offers a mild, efficient, and atom‐economical alternative to traditional chemical oxidants. This Review discusses advances in the field of transition metal‐electrocatalyzed C−H functionalization over the past decade and describes how the unique features of electricity enable metal‐catalyzed C−H functionalization in an economic and sustainable way.

A comparative overview of the electrochemical valorization and incorporation of CO2 in industrially relevant compounds

“…Alternatives for the halide-assisted metal reoxidation can be investigated, even towards direct metal reoxidation at the anode. [236][237][238] Furthermore, a lot of electrochemical protocols for DMC synthesis starting from CO as carbon source have been published. 228 Additionally, the electrochemical transformation of CO 2 to CO is also well established, with electrocatalysts analogously deposited on the cathode.…”

Frontiers in Photoelectrochemical Catalysis: A Focus on Valuable Product Synthesis

“…As a result, the feasibility of the process is a major concern, limiting it from being commercialized at a large scale. The past decades have witnessed the development of this reaction via several strategies, including photocatalysis, [ 141 ] electrocatalysis, [ 142 ] photoelectrocatalysis, [ 143 ] electrophotocatalysis, [ 144 ] and Hofman–Loffer–Ferytang reactions. [ 145 ] The photoelectrochemical activation and conversion of C─H and C─C bonds present several advantages, such as ease of product separation and less energy consumption.…”

Electrochemical Ruthenium‐Catalysed Directed C−H Functionalization of Arenes with Boron Reagents

“…The merging of electrochemistry with transitionmetal catalysis for CÀ H functionalization has made substantial progress in recent years for myriad transformations. [47][48][49][50] Key benefits include the avoidance of stoichiometric metal salt oxidants, instead using electricity as a "green oxidant" (Scheme 2), and access to milder reaction conditions which are more tolerant of sensitive substrates and coupling partners. Previous work by Chang and co-workers has shown that post-transmetalation intermediates of cyclometalated Ir, Rh, and Ru complexes can be prepared and isolated from respective aryl-and methylboronic coupling partners at mild temperature, which will undergo oxidatively induced reductive elimination to form a CÀ C bond once subjected to chemical or electrochemical oxidation.…”

“…The merging of electrochemistry with transition‐metal catalysis for C−H functionalization has made substantial progress in recent years for myriad transformations [47–50] . Key benefits include the avoidance of stoichiometric metal salt oxidants, instead using electricity as a “green oxidant” (Scheme 2), and access to milder reaction conditions which are more tolerant of sensitive substrates and coupling partners.…”