C−S Cross‐Coupling Reactions Catalyzed by Well‐Defined Copper and Nickel Complexes

Abstract

This review presents well-defined copper and nickel complexes that have been used in the formation of CÀ S bonds. The use of Cu or Ni catalysts represent an advantage in comparison with those based on precious metals such as Pd, by being two of the most abundant metals in the earth's crust and thus cheaper. As can be expected the catalytic activity of the different Cu and Ni complexes is strongly dependent on the nature of the ligands used. Thus, multidentate and strong electron-donating ligands are of common use to design highly active species since such ligands are capable to stabilize species in high oxidation states which are key intermediates in the reaction mechanisms of these processes. This being particular true in the case of copper, where Cu(III) produces unstable and reactive species that require an "extra stabilization" during the reaction mechanism. Hence, the reaction mechanisms using copper and nickel complexes as catalysts are also discussed in this paper, including the role of the different ligands during the catalytic processes. Although there is an increasing number of reports on CÀ S cross coupling reactions, due to the relevance of this transformation, they are often difficult to reproduce and not of general use since the actual catalytic species are not identified. Thus, we hope that this report will help to promote the search and synthesis of new ligands for the design of more active welldefined complexes that can be used as catalysts in a more rational manner in the formation of valuable CÀ S bondcontaining species.

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“…The deficiency of protons in the structures of different forms of coordinated ligand PLSC gives the possibility of using this ligand as a catalyst. It has been shown that organometallic copper and nickel complexes can be used as catalysts for C−S bond formation [ 13 ], and possible inhibitors of the main protease of SARS-CoV-2 [ 14 ].…”

Cross-Electrophile Coupling of Benzyl Halides and Disulfides Catalyzed by Iron

“…Synthetic applications showcase scalability, versatility, and downstream applications of the reported technology including product elaboration, drug synthesis, and a new mode of bioconjugation. The reported method marks a significant advance to the limited alternative transition-metal or post-transition-metal procedures requiring the use of stoichiometric reagents , or advancing only with activated coupling partners. , …”

“…The reported method marks a significant advance to the limited alternative transition-metal or post-transition-metal procedures requiring the use of stoichiometric reagents 39 , 40 or advancing only with activated coupling partners. 41 , 42 …”

Cobalt Coordination Polymers Offering Hydrogen Bonding Cavities as Efficient Catalysts for Coupling Reactions

“…[38] In recent times, carbon-carbon (CÀ C) bond forming reactions have generated ample interest, particularly the ones that are catalyzed by earth-abundant metals in a heterogeneous manner. [39][40][41] In this context, infinite dimensional CPs offer noteworthy opportunities. From a pool of CÀ C bond forming reactions, Michael addition reactions (MARs) have gained widespread attention.…”

“…In recent times, carbon‐carbon (C−C) bond forming reactions have generated ample interest, particularly the ones that are catalyzed by earth‐abundant metals in a heterogeneous manner [39–41] . In this context, infinite dimensional CPs offer noteworthy opportunities.…”