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首次运用密度泛函理论从分子水平上研究了铜(Ⅰ)催化烯丙基烷基化反应的机理。对所有可能反应路线的比较研究表明,[(i-Pr)2Cu]-在离去基团的对位与底物分子结合的同时,硫代磷酸酯从#-碳位解离。中间体$-烯丙基铜(Ⅲ)接着经异构化和还原消除过程形成#-或%-产物,#-取代是该反应的主要产物。理论计算研究结果与实验事实非常吻合。
The mechanism of allylation of copper (Ⅰ) catalyzed by Cu (Ⅰ) was first studied at the molecular level using density functional theory. A comparative study of all possible reaction routes showed that [(i-Pr) 2Cu] - at the para position of the leaving group bound to the substrate molecule, the phosphorothioate dissociates from the # -carbon position. The intermediate $ - allyl copper (III) then undergoes the isomerization and reductive elimination processes to form the # - or% products, which are the major products of the reaction. The theoretical calculation results are in good agreement with the experimental ones.