有机化学 ›› 2021, Vol. 41 ›› Issue (8): 3312-3320.DOI: 10.6023/cjoc202102050 上一篇    下一篇

研究简报

基于吡啶和1,3,5-三嗪的PNP钳状配体的设计合成以及在钴催化的末端炔烃半氢化反应中的应用

王银银, 林晓婉, 张飘, 沈美华, 徐华栋*(), 徐德锋*()   

  1. 常州大学药学院 江苏常州 213164
  • 收稿日期:2021-02-26 修回日期:2021-04-09 发布日期:2021-05-25
  • 通讯作者: 徐华栋, 徐德锋
  • 基金资助:
    国家自然科学基金(21672027); 江苏省高层次创新创业人才团队(2017-37)

Design and Synthesis of Pyridine and 1,3,5-Triazine PNP Pincer Ligands and Their Application in Cobalt Catalyzed Semihydrogenation of Terminal Alkynes

Yinyin Wang, Xiaowan Lin, Piao Zhang, Meihua Shen, Huadong Xu(), Defeng Xu()   

  1. School of Pharmacy, Changzhou University, Changzhou, Jiangsu 213164
  • Received:2021-02-26 Revised:2021-04-09 Published:2021-05-25
  • Contact: Huadong Xu, Defeng Xu
  • Supported by:
    National Natural Science Foundation of China(21672027); High-Level Entrepreneurial Talent Team of Jiangsu Province(2017-37)

设计并合成了两类新型的PNP钳状配体, 一类以吡啶结构为骨架, 另一类以1,3,5-三嗪结构为骨架. 将这两类配体应用于钴催化的硅氢还原末端炔烃N-(3-炔丁基)对甲苯磺酰胺(8a)的反应中, 发现两者对反应速率和选择性均有重大影响. 其中具有吸电子取代基的吡啶结构的配体2,6-双((S)-2-((二苯基膦)甲基)吡咯烷基)烟酸乙酯(L5b)可以高效促进8a的迁移半氢化反应, 主要给出反式内烯产物. 通过进一步筛选金属催化剂、溶剂和还原剂, 确定了获得反式内烯产物的最优反应条件为CoCl2/L5b/SiH(OMe)3/四氢呋喃(THF). 运用最优条件, 研究了另外8种末端炔烃8b~8i的迁移半氢化反应, 反应产物仍主要以反式内烯为主. 简而言之, 通过配体L5b发展了一种末端炔烃迁移还原的方法.

关键词: PNP钳状配体, 吡啶, 1,3,5-三嗪, 钴催化, 末端炔烃, 迁移半氢化反应, 反式内烯

Two types of novel PNP pincer ligands were designed and synthesized. One had a pyridine core and the other had a 1,3,5-triazine. Evaluation of these ligands in cobalt catalyzed semihydrogenation by silane of terminal alkyne N-(but-3- yn-1-yl)-4-methylbenzenesulfonamide (8a) was carried out, in which both had significant effects on the reaction rate and selectivity. Ethyl 2,6-bis((S)-2-((diphenylphosphanyl)methyl)pyrrolidin-1-yl)nicotinate (L5b), which had pyridine skeleton with electron-withdrawing substituent, promoted the migratory semihydrogenation of 8a giving E-2-alkene predominatly. Further screening of metal catalysts, solvents and reducing agents revealed that the optimal reaction condition was CoCl2/L5b/ SiH(OMe)3/trifluoroacetic acid (THF) for E-2-alkene product. More terminal alkynes 8b~8i were tested under the optimal reaction condition to afford E-2-alkene mainly. In brief, using ligand L5b, a method of migratory semihydrogenation of terminal alkynes was developed.

Key words: PNP pincer ligand, pyridine, 1,3,5-triazine, cobalt catalysis, terminal alkyne, migratory semihydrogenation, E-2-alkene