Uncovering a copper(II) Alkynyl Complex in C−C Bond Forming Reactions

Copper(II) alkynyl species are proposed as key intermediates in numerous Cu−catalysed C−C coupling reactions. Supported by a β−diketiminate ligand, the three coordinate copper(II) alkynyl [CuII]−C≡CAr (Ar = 2,6−Cl2C6H3) forms upon reaction of the alkyne H−C≡CAr with the copper(II) tert−butoxide complex [CuII]−OtBu. In solution, this [CuII]−C≡CAr species cleanly transforms the to the Glaser coupling product ArC≡C−C≡CAr and [CuI](solvent). Addition of nucleophiles R′C≡CLi (R′ = aryl, silyl) and Ph–Li to [CuII]−C≡CAr affords the corresponding Csp−Csp and Csp−Csp2coupled products RC≡C−C≡CAr and Ph–C≡CAr with concomitant generation of [CuI](solvent) and {[CuI]−C≡CAr}. Supported by DFT calculations, redox disproportionation forms [CuIII](C≡CAr)(R) species that reductively eliminate R−C≡CAr products. [CuII]−CCAr also captures the trityl radical Ph3C• to give Ph3C−C≡CAr. Radical capture represents the key Csp−Csp3 bond forming step in the copper catalysed C-H functionalization of benzylic substrates R−H with alkynes H−C≡CR′ (R′ = (hetero)aryl, silyl) that provide Csp−Csp3 coupled products R−C≡CR via radical relay with tBuOOtBu as oxidant.