Kong Deping, Wu Hongli, Ge Jiaao, Shen Zhen, Huang Genping
Department of Chemistry, School of Science and Tianjin Key Laboratory of Molecular Optoelectronic Sciences, Tianjin University, Tianjin 300072, P.R. China.
J Org Chem. 2022 May 6;87(9):6438-6443. doi: 10.1021/acs.joc.2c00305. Epub 2022 Apr 11.
Density functional theory calculations were performed to investigate the cobalt-catalyzed intermolecular hydroarylation/cyclization of 1,6-enynes with -pyridylindoles. The computations reveal that the reaction begins with the oxidative cyclization of 1,6-enyne to afford the five-membered cobaltacycle, from which the metal-assisted σ-bond metathesis/C-C reductive elimination led to the final hydroarylation/cyclization product. The initial oxidative cyclization constitutes the rate-determining step of the overall reaction. The steric repulsion and π···π interaction were found to play a crucial role in dictating the experimentally observed enantioselectivity.
进行了密度泛函理论计算，以研究钴催化的1,6-烯炔与β-吡啶基吲哚的分子间氢芳基化/环化反应。计算结果表明，反应始于1,6-烯炔的氧化环化，生成五元钴环，金属辅助的σ键复分解/C-C还原消除反应由此生成最终的氢芳基化/环化产物。最初的氧化环化是整个反应的速率决定步骤。发现空间排斥和π···π相互作用在决定实验观察到的对映选择性方面起着关键作用。
