Costentin Cyrille, Savéant Jean-Michel
Département de Chimie Moléculaire, Université Grenoble-Alpes, CNRS, UMR 5250 38000 Grenoble France
Université Paris Diderot, Sorbonne Paris Cité 75205 Paris Cedex 13 France.
Chem Sci. 2019 Nov 29;11(4):1006-1010. doi: 10.1039/c9sc05147c.
A recent remarkable study of the C-H oxidation of substituted fluorenyl-benzoates together with the transfer of a proton to an internal receiving group by means of electron transfer outer-sphere oxidants, in the noteworthy absence of hydrogen-bonding interactions, is taken as an example to uncover the existence of a mechanism crossover, making the reaction pass from a CPET pathway to a PTET pathway as the driving force of the global reaction decreases. This was also the occasion to stress that considerations based on "imbalanced" or "asynchronous" transition states cannot replace activation/driving force models based on the quantum mechanical treatment of both electrons and transferring protons.
最近一项关于取代芴基苯甲酸酯的C-H氧化以及通过电子转移外层氧化剂将质子转移到内部接受基团的显著研究，在值得注意的是不存在氢键相互作用的情况下，被用作一个例子来揭示一种机制交叉的存在，即随着全局反应驱动力的降低，反应从CPET途径转变为PTET途径。这也是一个强调基于“不平衡”或“异步”过渡态的考虑不能取代基于对电子和转移质子进行量子力学处理的活化/驱动力模型的时机。
