铜氢催化烯烃氢官能化区域选择性的起源。
Origins of Regioselectivity in CuH-Catalyzed Hydrofunctionalization of Alkenes.
机构信息
School of Chemistry and Chemical Engineering, Key Laboratory of Colloid and Interface Chemistry, Ministry of Education, Shandong University, Jinan, Shandong 250100, China.
Key Lab for Materials of Energy Conversion and Storage of Shanxi Province and Key Lab of Chemical Biology and Molecular Engineering of Ministry of Education, Institute of Molecular Science, Shanxi University, Taiyuan, Shanxi 030006, China.
出版信息
J Org Chem. 2023 Mar 3;88(5):2750-2757. doi: 10.1021/acs.joc.2c02296. Epub 2023 Feb 15.
Factors controlling the regioselectivity in alkene hydrocupration were computationally investigated using energy decomposition analysis. The results demonstrate that the Markovnikov-selective hydrocupration with electronically activated mono-substituted olefins is mostly affected by the destabilizing Pauli repulsion, which is due to the electron delocalization effect. The anti-Markovnikov-selective hydrocupration with 1,1-dialkyl-substituted terminal olefins is dominated by the repulsive electrostatic interactions, which is because of the unequal π electron distribution caused by the induction effect of alkyl substituents.
采用能量分解分析方法对烯烃水合反应区域选择性的控制因素进行了计算研究。结果表明，电子激活的单取代烯烃的马氏选择性水合主要受不稳定的 Pauli 排斥作用影响，这是由于电子离域效应所致。1,1-二取代末端烯烃的反马氏选择性水合主要受排斥静电相互作用的控制，这是由于烷基取代基的诱导效应导致π电子分布不均所致。
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