Computational explorations of mechanisms and ligand-directed selectivities of copper-catalyzed Ullmann-type reactions.

ABSTRACT: Computational investigations of ligand-directed selectivities in Ullmann-type coupling reactions of methanol and methylamine with iodobenzene by beta-diketone- and 1,10-phenanthroline-ligated Cu(I) complexes are reported. Density functional theory calculations using several functionals were performed on both the nucleophile formation and aryl halide activation steps of these reactions. The origin of ligand-directed selectivities in N- versus O-arylation reactions as described in a previous publication (J. Am. Chem. Soc. 2007, 129, 3490-3491) were studied and explained. The selectivities observed experimentally are derived not from initial Cu(I)(nucleophile) complex formation but from the subsequent steps involving aryl halide activation. The arylation may occur via single-electron transfer

SUBMITTER: Jones GO 

PROVIDER: S-EPMC2908497 | biostudies-literature | 2010 May

REPOSITORIES: biostudies-literature