Copper(I)-Catalyzed Synthesis of Azoles. DFT Study Predicts Unprecedented Reactivity and Intermediates

Fahmi Himo,† Timothy Lovell,† Robert Hilgraf,‡ Vsevolod V. Rostovtsev,‡ Louis Noodleman,*† K. Barry Sharpless,*‡ and Valery V. Fokin*‡; ;
Contribution from the Department of Molecular Biology, and Department of Chemistry and The Skaggs Institute for Chemical Biology, The Scripps Research Institute, 10550 North Torrey Pines Road, La Jolla, California 92037
J. Am. Chem. Soc., 2005, 127 (1), pp 210–216
DOI: 10.1021/ja0471525
Publication Date (Web): December 8, 2004
Copyright © 2005 American Chemical Society
†

 Department of Molecular Biology.

,
‡

 Department of Chemistry and The Skaggs Institute for Chemical Biology.

,
*

In papers with more than one author, the asterisk indicates the name of the author to whom inquiries about the paper should be addressed.

, fokin@scripps.edu, ; , sharples@scripps.edu, ; , lou@scripps.edu

Abstract

Abstract Image

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.

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History

  • Published In Issue January 12, 2005
  • Received May 14, 2004

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