Communication

Mechanistic Investigations of the Acid-Catalyzed Cyclization of a Vinyl ortho-Quinone Methide

  1. Lee M. Bishop1,
  2. Michael Winkler Dr.2,
  3. Kendall N. Houk Prof. Dr.3,
  4. Robert G. Bergman Prof. Dr.1,
  5. Dirk Trauner Prof. Dr.1

Article first published online: 30 APR 2008

DOI: 10.1002/chem.200800662

Issue

Chemistry - A European Journal

Chemistry - A European Journal

Volume 14, Issue 18, pages 5405–5408, June 20, 2008

Additional Information

How to Cite

Bishop, Lee M., Winkler, M., Houk, Kendall N., Bergman, Robert G. and Trauner, D. (2008), Mechanistic Investigations of the Acid-Catalyzed Cyclization of a Vinyl ortho-Quinone Methide. Chem. Eur. J., 14: 5405–5408. doi: 10.1002/chem.200800662

Author Information

  1. 1

    Department of Chemistry, University of California, Berkeley, Berkeley, CA 94720-1460, USA, Fax: (+1) 510-642-7714

  2. 2

    Institut für Organische Chemie, Universität Würzburg, Am Hubland, 97074 Würzburg, Fax: (+49) 931-888-4606

  3. 3

    Department of Chemistry and Biochemistry, University of California, Los Angeles, Los Angeles, CA 90095-1569, USA, Fax: (+1) 310-206-1843

Publication History

  1. Issue published online: 11 JUN 2008
  2. Article first published online: 30 APR 2008
  3. Manuscript Received: 8 APR 2008

Funded by

  • NSF. Grant Number: CHE-0233882
  • NSF. Grant Numbers: CHE-0345488, CHE-0548209

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Keywords:

  • activation parameters;
  • alkenes;
  • density functional calculations;
  • dimerization;
  • isomerization
Thumbnail image of graphical abstract

Acid-catalyzed and thermal cyclization of an isolable vinyl ortho-quinone methide has been kinetically and computationally investigated. We propose that both reactions proceed through rate-limiting exo-alkylidene bond isomerization followed by faster oxa-6π electrocyclization. The vinyl ortho-quinone methide was found to be surprisingly basic, allowing for quantitative protonation with relatively weak acids. In addition, we have identified a new mode of Diels–Alder dimerization of vinyl ortho-quinone methides.

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