Mechanistic study of asymmetric oxidative biaryl coupling: evidence for self-processing of the copper catalyst to achieve control of oxidase vs oxygenase activity

J Am Chem Soc. 2008 Sep 17;130(37):12232-3. doi: 10.1021/ja804570b. Epub 2008 Aug 19.

Abstract

Copper(I) and copper(II) 1,5-diaza-cis-decalin complexes [(N2)Cu] are effective precatalysts for aerobic oxidative coupling of naphthol substrates. Mechanistic studies, however, reveal that these complexes are not the reactive form of the catalyst under steady-state conditions. Rather, the active catalyst forms in a presteady-state self-processing step that involves oxygenation of the naphthol substrate. The oxygenated substrate, NapHOX, serves as a cofactor that combines with the (N2)Cu complexes to achieve highly selective, steady-state oxidase reactivity (aerobic oxidative biaryl coupling).

Publication types

  • Research Support, N.I.H., Extramural
  • Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

  • Catalysis
  • Copper / chemistry*
  • Heterocyclic Compounds, 2-Ring / chemistry
  • Kinetics
  • Naphthols / chemical synthesis*
  • Naphthols / chemistry
  • Organometallic Compounds / chemistry
  • Oxidation-Reduction
  • Oxidoreductases / chemistry*
  • Oxidoreductases / metabolism
  • Oxygenases / chemistry*
  • Oxygenases / metabolism
  • Piperidines / chemistry

Substances

  • 1,5-diazadecalin
  • Heterocyclic Compounds, 2-Ring
  • Naphthols
  • Organometallic Compounds
  • Piperidines
  • Copper
  • Oxidoreductases
  • Oxygenases