Recent Advances in Metal-Catalyzed, Electrochemical Coupling Reactions of sp2 Halides/Boronic Acids and sp3 Centers

Abstract

Traditionally, metal-catalyzed cross-coupling reactions rely on stable but expensive metals, such as palladium. However, the recent development of synthetic organic electrochemistry allows for in situ redox manipulations, expanding the use of cheaper, abundant and sustainable metals, such as nickel and copper as efficient cross-coupling catalysts. This short review covers the recent advances in metal-catalyzed electrochemical coupling reactions, with a focus on reactions of sp2 electrophiles and nucleophiles with sp3 coupling partners to form both C–C and C–heteroatom bonds.1 Introduction2 Nickel-Catalyzed C–C sp2–sp3 Coupling Reactions3 Coupling of Aryl Groups with Heteroatomic Nuclei4 Conclusion

Nickel-Catalyzed Paired Electrochemical Cross-Coupling of Aryl Halides with Nucleophiles

“…17,18 However, many challenges and opportunities still remain in this area, including how to further improve the efficiency, atom economy, selectivity, as well as expanding the scope of the reactions. One of the key strategies in expanding the chemical space of this area is to merge transition-metal ca-talysis with other fields, such as radical chemistry, 19 electrochemistry, 20,21 as well as photochemistry, 22 thereby expanding the scope of the coupling components and the reaction modes.…”

Recent Advances in the Nickel‐catalysed Electrochemical Coupling Reactions with a Focus on the Type of Bond Formed

“…Cross‐coupling reactions employing transition metals have historically been used extensively as powerful, targeted, and high‐yielding methods in synthetic chemistry [1–6] . Electrochemical metal catalysis has recently drawn substantial attention as an enabling technology for modern synthetic chemistry [7,8] . This approach represents an eco‐friendly and economically viable method, as the electric current can controllably stimulate the development of reactive intermediates and catalysts, without the use of external oxidizing or reducing agents [9] and it is more selective, produces less trash, and operates under moderate circumstances [10] .…”

“…[1][2][3][4][5][6] Electrochemical metal catalysis has recently drawn substantial attention as an enabling technology for modern synthetic chemistry. [7,8] This approach represents an eco-friendly and economically viable method, as the electric current can controllably stimulate the development of reactive intermediates and catalysts, without the use of external oxidizing or reducing agents [9] and it is more selective, produces less trash, and operates under moderate circumstances. [10] Although palladium-catalysed processes are extremely beneficial, [11][12][13] there have been growing concerns about the environmental and economic effects of their extensive usage.…”

Selective Synthesis of Ketones and Chiral Allylic Alcohols from the Addition of Arylboronic Acids to α,β-Unsaturated Aldehydes Mediated by a Transition Metal/Monophosphorus Ligand System

“…Compared with hydroboration and 1,2-addition with organometallic reagents, arylboronic acids are stable and nontoxic and can be used under relatively mild reaction conditions . The addition of boric acid to α,β-unsaturated aldehydes is also an effective method of preparing ketones or alcohols.…”