【摘要】 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。更多还原

【Abstract】 The mechanism of the Cu( Ⅰ)-catalyzed allylic alkylation at the molecular-level was explored using density functional theory( DFT). A comprehensive comparison of all possible reaction pathways shows that [( i-Pr) 2 Cu]-prefers to bind oxidatively to the double bond of the allylic substrate at the anti-position with respect to the leaving group,followed by the dissociation of the leaving group. The key intermediate $-allylcopper( Ⅲ) then undergoes an isomerization and a reductive elimination process to give #-or %-product. #-product is the main product of this reaction. The computational results are in good agreement with experimental findings.更多还原