Bifurcations on potential energy surfaces of organic reactions.
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.
Ess
Daniel H
DH
Department of Chemistry and Biochemistry, University of California, Los Angeles, 607 Charles E. Young Drive East, Los Angeles, CA 90095, USA.
Wheeler
Steven E
SE
Iafe
Robert G
RG
Xu
Lai
L
Celebi-Olçüm
Nihan
N
Houk
Kendall N
KN