Jiangsu Key Laboratory of Pesticide Science, College of Sciences, Nanjing Agricultural University, Nanjing, 210095, People's Republic of China.
J Mol Model. 2021 May 4;27(5):150. doi: 10.1007/s00894-021-04773-6.
The reaction mechanism of Pd-catalyzed regioselective C-H alkylation of indole with MesICHCFOTf has been investigated by the density functional theory calculations. The reaction mechanism mainly contains four steps: C-H activation, oxidative addition, reductive elimination, and ligands substitution. From our calculations, we find that the C-H activation step was realized by the acetate anion (OAc) assisted concerted metalation deprotonation (CMD) process and the transition state of C-H activation process is a square planar configuration. Moreover, the calculation results suggest that the regioselectivity of C-H bond alkylation of indole with MesICHCFOTf can be ascribed to the different stability of the CMD transition states in C-H activation step and the relative stabilities of deprotonated intermediates.
钯催化吲哚与 MesICHCFOTf 的区域选择性 C-H 烷基化反应的反应机理通过密度泛函理论计算进行了研究。反应机理主要包含四个步骤：C-H 活化、氧化加成、还原消除和配体取代。根据我们的计算，我们发现 C-H 活化步骤是通过醋酸根阴离子（OAc）辅助的协同金属化去质子化（CMD）过程实现的，C-H 活化过程的过渡态为平面四方构型。此外，计算结果表明，吲哚与 MesICHCFOTf 的 C-H 键烷基化的区域选择性可以归因于 C-H 活化步骤中 CMD 过渡态的不同稳定性和去质子化中间体的相对稳定性。
