高等学校化学学报

高等学校化学学报 ›› 2003, Vol. 24 ›› Issue (11): 2031.

• 论文 • 上一篇    下一篇

顺-8-三甲基锡烷基-6-辛烯醛分子内环化反应立体选择性的理论研究

徐开来1, 谢代前1,2, 鄢国森1   

  1. 1. 四川大学化学学院, 成都 610064;
    2. 南京大学理论与计算化学研究所, 化学系, 南京 210093
  • 收稿日期:2003-02-18 出版日期:2003-11-24 发布日期:2003-11-24
  • 通讯作者: 谢代前(1964年出生),男,博士,教授,博士生导师,主要从事分子激发态及动力学理论研究.E-mail:dqxie@nju.edu.cn E-mail:dqxie@nju.edu.cn
  • 基金资助:

    国家自然科学基金(批准号:20173036);教育部高校青年教师奖资助;南京大学引进人才启动基金资助

Theoretical Studies on the Intramolecular Cyclization of (Z)-8-(Trimethylstannyl)oct-6-enal

XU Kai-Lai1, XIE Dai-Qian1,2, YAN Guo-Sen1   

  1. 1. College of Chemistry, Sichuan University, Chengdu 610065, China;
    2. Institute of Theoretical and Computational Chemistry, Department of Chemistry, Nanjing University, Nanjing 210093, China
  • Received:2003-02-18 Online:2003-11-24 Published:2003-11-24

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摘要： 用密度泛函方法在B3LYP/6-31G*水平上研究了顺-8-三甲基锡烷基-6-辛烯醛分子内环化反应的机理,通过振动分析和内禀反应坐标对过渡态进行了确认,解析了三种反应途径.结果表明,反应具有很强的立体选择性,虽然-OSn(CH3)3和-C2H3基团均处于环的平伏位,是最稳定的产物构型,但是主要产物是经过活化能最低,且具有两个六元环椅式构象的过渡态形成的,主要产物中-OSn(CH3)3基团处于环的直立位.该结果与实验事实一致.

关键词: 顺-8-三甲基锡烷基-6-辛烯醛, 环化反应, 立体选择性, B3LYP

Abstract: The intramolecular cyclization of (Z)-8-(trimethylstannyl)oct-6-enal were studied by using the density functional method at the B3LYP/6-31G*level.The structures and energies of the stationary points were calculated to produce the activation barriers.The transition states were testified by using vibration analysis and IRC calculations.Three reaction pathways were analyzed.All the reactions are the exothermic reations and the concerted reaction processes which have only one double-six-membered transition state dominated by the Cl-C6 vibration.Each of the reactions progresses with the bond formation of Sn10-O9 and C1-C6, the bond breaking of C8-Sn10 and the migration of the diene double bond to form the six-membered cyclic product.The results show that the reaction occurs with a high stereoselectivity.The product, in which both-OSn(CH3)3and-C2H3moieties are at the equatorial position, is the most stable one among three reactions, whereas the mainly product is obtained through the double-six-membered chairlike conformational transition state with the lowest barrier height.ThiSISIn excellent {agreement} with the experimental results.

Key words: (Z)-8-(Trimethylstannyl)oct-6-enal, Cyclization, Stereoselectivity, B3LYP

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