有机化学 ›› 2018, Vol. 38 ›› Issue (5): 1138-1146.DOI: 10.6023/cjoc201712039 上一篇    下一篇

研究论文

四嗪化合物与环辛炔的[4+2]环加成反应及其在构建轴手性哒嗪骨架中的应用

蔡正军a, 高建保b, 李白a, 钟源a, 丰幸a, 薛吉军c, 蒋先兴a   

  1. a 中山大学药学院 广州 510006;
    b 山东汉兴医药科技有限公司 昌邑 261312;
    c 兰州大学化学化工学院 兰州 730000
  • 收稿日期:2017-12-27 修回日期:2018-01-29 发布日期:2018-02-11
  • 通讯作者: 薛吉军,E-mail:jiangxx5@mail.sysu.edu.cn;蒋先兴,E-mail:xuejj@lzu.edu.cn E-mail:jiangxx5@mail.sysu.edu.cn;xuejj@lzu.edu.cn
  • 基金资助:

    国家自然科学基金(Nos.91413107,21432003)、“青年千人”计划及中央高校基本科研业务费专项资金(No.lzujbky-2014-61)资助项目.

Application of [4+2]Cycloaddition Reaction of Tetrazine with Cyclooctyne in the Construction of Pyridazine Structure with Axial Chirality

Cai Zhengjuna, Gao Jianbaob, Li Baia, Zhong Yuana, Feng Xinga, Xue Jijunc, Jiang Xianxinga   

  1. a School of Pharmaceutical Sciences, Sun Yat-Sen University, Guangzhou 510006;
    b Shandong Hanxing Medical Technology Co., Ltd., Changyi 261312;
    c College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000
  • Received:2017-12-27 Revised:2018-01-29 Published:2018-02-11
  • Contact: 10.6023/cjoc201712039 E-mail:jiangxx5@mail.sysu.edu.cn;xuejj@lzu.edu.cn
  • Supported by:

    Project supported by the National Natural Science Foundation of China (Nos. 91413107, 21432003), the Thousand Young Talents Program and the Fundamental Research Funds for the Central Universities of China (No. lzujbky-2014-61).

探究了四嗪化合物和环辛炔的[4+2]环加成反应及其在构建轴手性哒嗪骨架中的应用.在不加催化剂的条件下,具有空间位阻的四嗪化合物和大环张力的环辛炔能够在二氯甲烷中发生反电子需求的Diels-Alder反应.反应经历六元桥环过渡态,在温和的条件下脱去一分子氮气,得到具有哒嗪骨架结构的轴手性化合物.该反应能够通过颜色的变化判断反应转化情况,能以很高的产率(95%)得到具有潜轴手性的哒嗪骨架产物.

关键词: 四嗪化合物, 轴手性, 反电子需求Diels-Alder反应, 环辛炔

The application of [4+2] cycloaddition reaction of tetrazine with cyclooctyne in the construction of pyridazine structure with axial chirality was studied. The inverse electronic demand Diels-Alder reaction of tetrazine bearing bulky groups with macrocyclic tension’s cyclooctyne could take place under catalyst-free conditions in dichloromethane. The reaction underwent a six-membered bridged transition state, gently release a molecule of nitrogen to get axial chiral pyridazine structure. The transformation of the reaction can be determined by the change of color. The reaction could get potential axial chiral pyridazine structure with high yiled (95%) under mild conditions.

Key words: tetrazine, axial chirality, the inverse electronic demand Diels-Alder reaction, cyclooctyne