铜(Ⅰ)催化硫代磷酸酯的烯丙基烷基化机理的理论研究  

Theoretical study on mechanism of Cu( Ⅰ)-catalyzed allylic alkylation of phosphorothioate esters

作　　者：严志伟[1] 盛文浩[1] 王坚毅[1] 

机构地区：[1]广西大学化学化工学院,广西南宁530004

出　　处：《广西大学学报（自然科学版）》2013年第6期1346-1351,共6页Journal of Guangxi University（Natural Science Edition）

基　　金：国家自然科学基金资助项目(21262004)

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。The mechanism of the Cu（ I ）-catalyzed allylic alkylation at the molecular-level was ex- plored using density functional theory （DFT）. A comprehensive comparison of all possible reaction pathways shows that [ （i-Pr）2Cu]-prefers to bind oxidatively to the double bond of the allylic sub- strate at the anti-position with respect to the leaving group, followed by the dissociation of the leav- ing group. The key intermediate n-allylcopper（ Ill ） then undergoes an isomerization and a reductive elimination process to give a- or/-product, a-product is the main product of this reaction. The com- putational results are in good agreement with experimental findings.

关 键 词：区域选择性 烯丙基烷基化 铜(I)催化剂 密度泛函理论 

分 类 号：O641.12[理学—物理化学]