Abstract
Copper-catalyzed and organocopper-involved reactions are of great significance in organic synthesis. To have a deep understanding of the reaction mechanisms, the structural characterizations of organocopper intermediates become indispensable. Meanwhile, the structure-function relationship of organocopper compounds could advance the rational design and development of new Cu-based reactions and organocopper reagents. Compared to the mono-carbonic ligand, the C,N- and C,C-bidentate ligands better stabilize unstable organocopper compounds. Bidentate ligands can chelate to the same copper atom via η2-mode, forming a mono-cupra-cyclic compounds with at least one acute C-Cu-C angle. When the bidentate ligands bind to two copper atoms via η1-mode at each coordinating site, the bimetallic macrocyclic compounds will form nearly linear C-Cu-C angles. The anionic coordinating sites of the bidentate ligand can also bridge two metals via μ2-mode, forming organocopper aggregates with Cu-Cu interactions and organocuprates with contact ion pair structures. The reaction chemistry of some selected organocopper compounds is highlighted, showing their unique structure–reactivity relationships.
Highlights
Copper-mediated or -catalyzed reactions have been upgrading the toolbox of organic synthesis with a variety of cheap, efficient transformations, which benefit scientific research in a broad range of areas, such as in polymer chemistry and biochemistry [1,2,3,4,5,6,7,8,9,10,11,12]
The substituents of the can be regarded as variants of 44 by replacing the two lateral lithium atoms with copper butadienyl skeleton seem to have an influence on the stability of their copper clusters
We have summarized the structurally well-defined organocopper compounds based on C,N- and C,C-bidentate ligands, from mononuclear copper spiro compounds to polynuclear copper clusters
Summary
Copper-mediated or -catalyzed reactions have been upgrading the toolbox of organic synthesis with a variety of cheap, efficient transformations, which benefit scientific research in a broad range of areas, such as in polymer chemistry and biochemistry [1,2,3,4,5,6,7,8,9,10,11,12]. Methylcopper [24] and phenylcopper [26] clusters display rapid and slow decompositions at room temperature, respectively, while (phenylethynyl)copper [27] looks stable under ambient conditions This stability trend could be reflected by the numbers of singlecrystal structures in the Cambridge Structural Database (CSD 5.42, 2020 November), in which roughly 185 alkyl, 288 aryl, and 326 alkynyl copper compounds have been collected. Xi’s group discovered that 1,4-dilithio 1,3-butadienes (C,C-bidentate ligand) can stabilize reactive organocopper species to a great extent via a cooperative effect [30,31]. Mononuclear organocopper complexes: The two coordinating sites of the C,C- and C,N-bidentate ligand bind to the same Cu center together, forming a 5-membered chelate ring, as shown in (I) of Scheme 1.
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