欢迎访问中国科学院大学学报,今天是

中国科学院大学学报 ›› 2013, Vol. 30 ›› Issue (2): 187-193.DOI: 10.7523/j.issn.1002-1175.2013.02.007

• 化学与生命科学 • 上一篇    下一篇

苯基取代的六元碳链双烯酮阴离子自由基的分子内环加成反应的理论研究

袁建华, 陈波珍   

  1. 中国科学院研究生院化学与化学工程学院, 北京 100049
  • 收稿日期:2012-03-15 修回日期:2012-03-23 发布日期:2013-03-15
  • 通讯作者: 陈波珍
  • 基金资助:

    国家自然科学基金(21173262)和中国科学院研究生院院长基金资助

Theoretical study on the radical anion cycloaddition of six-carbon tethers phenyl-substituent bis(enone)

YUAN Jian-Hua, CHEN Bo-Zhen   

  1. College of Chemistry and Chemical Engineering, Graduate University, Chinese Academy of Sciences, Beijing 100049, China
  • Received:2012-03-15 Revised:2012-03-23 Published:2013-03-15

摘要:

用密度泛函理论B3LYP方法,结合6-31G(d,p)和6-311+G(d,p)基组,研究苯基取代的六元碳链双烯酮阴离子自由基的分子内环加成反应.探讨反应物分别通过[4+2]和[2+2]环加成反应生成六元环产物(i)和四元环产物(ii)的反应机理.结果表明,2个反应都是分步进行的,都先经过第1个过渡态得到中间体.然后从该中间体出发,反应(i)经过第2个过渡态得到六元环产物;反应(ii)经过另外一个过渡态得到四元环产物.计算表明反应(i)是主反应通道.

关键词: 密度泛函理论, 双烯酮, 环加成反应, 阴离子自由基

Abstract:

DFT B3LYP calculations with the 6-31G(d, p) and 6-311+G(d, p) basis sets were carried out to investigate the mechanisms of intramolecular cycloaddition of six-carbon tethers phenyl-substituent bis(enone). Both the hetero-Diels-Alder cycloaddult (da-P-) and the cis-cyclobutanation are predicted to be possible products of the reactions via radical anion. Our calculations also indicate that the da-P- is the dominant product both dynamically and thermodynamically, via a six-membered ring intermediate and two transition states.

Key words: DFT, bis(enone), cycloaddition, radical anion

中图分类号: