Bifurcations on Potential Energy Surfaces of Organic Reactions

Authors

  • Daniel H. Ess Dr.,

    1. Department of Chemistry and Biochemistry, University of California, Los Angeles, 607 Charles E. Young Drive East, Los Angeles, CA 90095 (USA), Fax: (+1) 310-206-1843
    Search for more papers by this author
  • Steven E. Wheeler Dr.,

    1. Department of Chemistry and Biochemistry, University of California, Los Angeles, 607 Charles E. Young Drive East, Los Angeles, CA 90095 (USA), Fax: (+1) 310-206-1843
    Search for more papers by this author
  • Robert G. Iafe,

    1. Department of Chemistry and Biochemistry, University of California, Los Angeles, 607 Charles E. Young Drive East, Los Angeles, CA 90095 (USA), Fax: (+1) 310-206-1843
    Search for more papers by this author
  • Lai Xu,

    1. Department of Chemistry and Biochemistry, University of California, Los Angeles, 607 Charles E. Young Drive East, Los Angeles, CA 90095 (USA), Fax: (+1) 310-206-1843
    Search for more papers by this author
  • Nihan Çelebi-Ölçüm,

    1. Department of Chemistry and Biochemistry, University of California, Los Angeles, 607 Charles E. Young Drive East, Los Angeles, CA 90095 (USA), Fax: (+1) 310-206-1843
    Search for more papers by this author
  • Kendall N. Houk Prof. 

    1. Department of Chemistry and Biochemistry, University of California, Los Angeles, 607 Charles E. Young Drive East, Los Angeles, CA 90095 (USA), Fax: (+1) 310-206-1843
    Search for more papers by this author

Abstract

A single transition state may lead to multiple intermediates or products if there is a post-transition-state reaction pathway bifurcation. These bifurcations arise when there are sequential transition states with no intervening energy minimum. For such systems, the shape of the potential energy surface and dynamic effects, rather than transition-state energetics, control selectivity. This Minireview covers recent investigations of organic reactions exhibiting reaction pathway bifurcations. Such phenomena are surprisingly general and affect experimental observables such as kinetic isotope effects and product distributions.

Ancillary