手性二噁唑啉铜不对称催化烯丙基氧化酰化反应的密度泛函研究  

Density Functional Theory Studies on Catalytic Enantioselective AllylicAcyloxylation of Olefins with Chiral Copper (I) Complexes and Tert-Butyl Perbenzoate

作　　者：黄浩[1] 翟巧玲[1] 吕文阳[1] 李明[1] 

机构地区：[1]西南大学化学化工学院,重庆400715

出　　处：《西南师范大学学报（自然科学版）》2006年第2期92-98,共7页Journal of Southwest China Normal University(Natural Science Edition)

基　　金：教育部重点研究项目(104263).

摘　　要：用密度泛函理论(DFT)研究了手性二嗯唑啉铜(I)催化过苯甲酸异丁酯与丁烯不对称烯丙基氧化酰化反应的机理．分别在B3LYP／6—31G,B3LYP／6—31G(d)水平上优化了反应中间体和过渡态的结构．结果表明,该反应是放热的．其中催化剂-苯甲酸丁烯酯手性加合物的生成是反应产物的手性决定步骤．理论预测的主要产物是s型苯甲酸-3-丁烯-2-酯,与实验吻合．The chiral bisoxazoline-copper（Ⅰ）-catalyzed asymmetric allylic acyloxylation of olefins and tertbutyl perbenzoate was studied by density functional theory （DFT）. All the intermediates and the transition states were optimized completely at the B3LYP/6-31G and B3LYP/6-31G（d） levels. As shown, this asymmetric allylic oxidation is exothermic. The turnoverdim formation of chiral catalyst-allyl perbenzoate complexes. but-3-en-2-yl benzoate, which is iting Th step for the asymmetric allylic oxidation is the e dominant product predicted theoretically is Sin agreement with the experiment.

关 键 词：手性二嗯唑啉铜催化剂 不对称催化 反应机理 密度泛函理论(DFT) 

分 类 号：O641[理学—物理化学]