有机化学 ›› 2019, Vol. 39 ›› Issue (6): 1655-1664.DOI: 10.6023/cjoc201903050 上一篇    下一篇

所属专题: 碳氢活化合辑2018-2019 金属有机化学

研究论文

碳钯化/C-H烯基化串联反应:含氧化吲哚类结构单元的轴手性烯基芳烃的不对称合成

杨云a, 刘慧慧a, 刘小兵a, 刘田田b, 朱玉芹b, 张安安b, 王涛b, 华远照c, 王敏灿c, 毛国梁a, 刘澜涛b,c   

  1. a 东北石油大学化学化工学院 大庆 163318;
    b 商丘师范学院化学化工学院 商丘 476000;
    c 郑州大学化学与分子工程学院 郑州 450001
  • 收稿日期:2019-03-24 修回日期:2019-05-10 发布日期:2019-05-15
  • 通讯作者: 毛国梁, 刘澜涛 E-mail:liult05@iccas.ac.cn;maoguoliang@nepu.edu.cn
  • 基金资助:

    国家自然科学基金(No.21572126)、河南省高校科技创新人才基金(No.14HASTIT016)、河南省科技创新杰出人才(No.2018JQ0011)资助项目.

Asymmetric Synthesis of Axial Chiral Vinylarenes Fearturing Oxindole Moiety via Tandem Carbopalladation/C-H Olefination

Yang Yuna, Liu Huihuia, Liu Xiaobinga, Liu Tiantianb, Zhu Yuqinb, Zhang Ananb, Wang Taob, Hua Yuanzhaoc, Wang Mincanc, Mao Guolianga, Liu Lantaob,c   

  1. a College of Chemistry and Chemical Engineering, Northeast Petroleum University, Daqing 163318;
    b College of Chemistry and Chemical Engineering, Shangqiu Normal University, Shangqiu 476000;
    c College of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou 450001
  • Received:2019-03-24 Revised:2019-05-10 Published:2019-05-15
  • Contact: 10.6023/cjoc201903050 E-mail:liult05@iccas.ac.cn;maoguoliang@nepu.edu.cn
  • Supported by:

    Project supported by the National Natural Science Foundation of China (No. 21572126), the Program for Science & Technology Innovation Talents in Universities of Henan Province (No. 14HASTIT016) and the Program of Science and Technology Innovation Talents of Henan Province (No. 2018JQ0011).

由于较低的旋转能垒,轴手性烯基芳烃衍生物的催化不对称合成存在很大挑战.氧化吲哚是天然产物的重要骨架,也是生物活性分子及药物的重要合成子.作者通过碳钯化/C-H键的烯基化串联反应实现了含氧化吲哚类结构单元的轴手性烯基芳烃的不对称合成.(4R,5R)-2,2-二甲基-α,α,α',α'-四苯基-1,3-二氧戊环-4,5-二甲醇(TADDOL)衍生的亚膦酰胺配体给出了较好的产率和中等的对映选择性.产物在110℃加热10 h后ee值没有降低,表明其手性轴具有很好的热稳定性.

关键词: 不对称合成, 轴手性, 烯基芳烃, 碳钯化, C-H键烯基化, 氧化吲哚

Due to the lower configuration stability of vinylarenes, arsing from the relatively lower rotational barriers, their catalytic asymmetric synthesis remains a daunting task. Oxindoles moiety are privileged framework of natural products and building blocks of bioactive molecules as well as pharmaceuticals. The asymmetric synthesis of axial chiral vinylarenes fearturing oxindole moiety via sequential carbopalladation/C-H olefination from readily available materials with palladium catalysis has been developed. (4R,5R)-(-)-2,2-Dimethyl-α,α,α',α'-tetraphenyl-1,3-dioxolane-4,5-dimethanol (TADDOL)-derived phosphoramidite gave products with good yield and moderate ee value. The erosion of optical purity was not observed even after heating the product for 10 h at 110℃, which indicates the excellent stability of the chiral axial.

Key words: asymmetric synthesis, axial chirality, vinyl-arenes, carbopalladation, C-H olefination, oxindole