Cheng Gui-Juan, Song Li-Juan, Yang Yun-Fang, Zhang Xinhao, Wiest Olaf, Wu Yun-Dong
Lab of Computational Chemistry and Drug Design, Laboratory of Chemical Genomics, Peking University Shenzhen Graduate School, Shenzhen 518055 (P. R. China).
Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, IN 46556 (USA).
Chempluschem. 2013 Sep;78(9):943-951. doi: 10.1002/cplu.201300117. Epub 2013 Jun 21.
A detailed computational study of a copper-catalyzed aerobic cross-dehydrogenative coupling reaction has been conducted. To select a reliable method to describe the thermochemistry of a single electron transfer (SET) process, benchmark calculations have been performed. M06/6-311+g(d,p) is appropriate to evaluate the thermochemistry of the SET process for the system involving iminium species. The computational results support an SET mechanism, but also uncover an alternative mechanism in which O is directly involved in a hydrogen-abstracting step. A comparative study with tert-butylhydroperoxide (TBHP) as the oxidant has also been performed. The computations reveal several competitive pathways, including a radical pathway, a Cu pathway, and an SET mechanism for the Cu/TBHP system.
已对铜催化的需氧交叉脱氢偶联反应进行了详细的计算研究。为了选择一种可靠的方法来描述单电子转移（SET）过程的热化学，已进行了基准计算。M06/6-311+g(d,p)适用于评估涉及亚胺离子物种的体系中SET过程的热化学。计算结果支持SET机理，但也揭示了一种O直接参与氢提取步骤的替代机理。还进行了以叔丁基过氧化氢（TBHP）为氧化剂的对比研究。计算结果揭示了几种竞争途径，包括自由基途径、Cu途径以及Cu/TBHP体系的SET机理。
