Copper(I)-catalyzed synthesis of azoles. DFT study predicts unprecedented reactivity and intermediates

J Am Chem Soc. 2005 Jan 12;127(1):210-6. doi: 10.1021/ja0471525.

Abstract

Huisgen's 1,3-dipolar cycloadditions become nonconcerted when copper(I) acetylides react with azides and nitrile oxides, providing ready access to 1,4-disubstituted 1,2,3-triazoles and 3,4-disubstituted isoxazoles, respectively. The process is highly reliable and exhibits an unusually wide scope with respect to both components. Computational studies revealed a stepwise mechanism involving unprecedented metallacycle intermediates, which appear to be common for a variety of dipoles.

Publication types

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

MeSH terms

  • Catalysis
  • Cations, Monovalent
  • Copper / chemistry*
  • Isoxazoles / chemical synthesis*
  • Models, Molecular
  • Nitriles / chemistry
  • Thermodynamics
  • Triazoles / chemical synthesis*

Substances

  • Cations, Monovalent
  • Isoxazoles
  • Nitriles
  • Triazoles
  • Copper