Ess Daniel H, Wheeler Steven E, Iafe Robert G, Xu Lai, Celebi-Olçüm Nihan, Houk Kendall N
Department of Chemistry and Biochemistry, University of California, Los Angeles, 607 Charles E. Young Drive East, Los Angeles, CA 90095, USA.
Angew Chem Int Ed Engl. 2008;47(40):7592-601. doi: 10.1002/anie.200800918.
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.
如果存在过渡态后反应途径分支，单一过渡态可能会导致多种中间体或产物。当存在连续的过渡态且其间没有能量最小值时，就会出现这些分支。对于此类体系，势能面的形状和动力学效应而非过渡态能量学控制选择性。本综述涵盖了对表现出反应途径分支的有机反应的近期研究。此类现象出奇地普遍，并影响诸如动力学同位素效应和产物分布等实验观测结果。
