Cobalt-mediated [2+2+2] cycloaddition versus C-H and N-H activation of 2-pyridones and pyrazinones with alkynes: A theoretical study

DFT computations have been executed aimed at illuminating the variety of pathways by which pyridones react with alkynes in the presence of [CpCoL2]: NH-2-pyridones furnish N-dienylated ligands (N-H activation pathway), N-methyl-2-pyridones are converted into ligated cyclohexadienes ([2+2+2] cocycloaddition pathway), and N-alkynyl-2-pyridones may undergo either [2+2+2] cocycloaddition or C-dienylation (C-H activation), depending on the length of the tether.The calculations predict the formation of the experimentally observed products, including their regio- and stereochemical make up. In addition, the unusual regiochemical outcome of the all-intramolecular [2+2+2] cycloaddition of N,N '-dipentynylpyrazinedione was rationalized by computation, which led to the discovery of a new mechanism.