Copper catalysed Gomberg-Bachmann-Hey reactions of arenediazonium tetrafluoroborates and heteroarenediazonium o-benzenedisulfonimides. Synthetic and mechanistic aspects. Issue 47 (20th November 2020)

• Record Type: Journal Article
• Authors: Antenucci, Achille; Barbero, Margherita; Dughera, Stefano; Ghigo, Giovanni
• Is Part Of: Tetrahedron. Volume 76:Issue 47(2020)
• Publication Date: 2020-11-20
• Subjects: Diazonium salts -- Gomberg-Bachmann-Hey reaction -- Copper catalysis -- Mechanistic studies -- C–H bond Activation; Chemistry, Organic -- Periodicals; 547.005
• DOI: 10.1016/j.tet.2020.131632
• Languages: English
• ISSNs: 0040-4020

Abstract

Abstract: Gomberg-Bachmann-Hey reactions were carried out in the presence of copper as a catalyst and gave rise to biaryls or heterobiaryls in good yields and in mild reaction conditions. A computational study of some key points of the reaction was performed. The results are coherent with the experimental data and confirm some aspects of the mechanism. The reaction free energies for the reduction in benzene by CuI of a set of 40 (hetero)arenediazonium tetrafluoroborates were calculated. Both the experiments and the calculations showed that in the coupling with substituted solvents (toluene, bromobenzene, nitrobenzene and anisole) the binding to the ortho position was always favoured. Graphical abstract: Image 1 Highlights: Gomberg-Bachmann-Hey reactions were carried out in the presence of copper as a catalyst. Good yields of biaryls or heterobiaryls in mild reaction conditions. Computational study of some key points of the reaction. Aryl radicals are key intermediates to generate the target products.