State Key Laboratory of Elemento-organic Chemistry, College of Chemistry, Nankai University, Collaborative Innovation Center of Chemical Science and Engineering , Tianjin 300071, P.R. China.
Department of Chemistry and Biology, College of Science, National University of Defense Technology , Changsha 410073, China.
J Org Chem. 2017 Sep 15;82(18):9321-9327. doi: 10.1021/acs.joc.7b01130. Epub 2017 Aug 29.
The sources of asymmetric induction in the photoinduced phase-transfer-catalytic perfluoroalkylation of β-ketoesters were interpreted by density functional theory calculations. The calculations indicated that multiple hydrogen-bonding interactions mode rather than π-π stacking interactions model better described the transition structure of the reaction. The quantitative estimation of these noncovalent interactions within the key transition states identified that the O-H···O and specific C-H···O hydrogen bonds play key roles for the stereocontrol.
通过密度泛函理论计算解释了光诱导相转移催化全氟烷基化β-酮酯中不对称诱导的来源。计算表明，多氢键相互作用模式而不是π-π堆积相互作用模型更好地描述了反应的过渡态。在关键过渡态中对这些非共价相互作用的定量估计表明，O-H···O 和特定的 C-H···O 氢键对于立体控制起着关键作用。
