高等学校化学学报 ›› 2020, Vol. 41 ›› Issue (12): 2766-2773.doi: 10.7503/cjcu20200420

• 有机化学 • 上一篇    下一篇

胺基膦钌卡宾化合物的合成及催化烯烃复分解反应

王晋宇, 柳春丽, 陈延辉()   

  1. 天津科技大学化工与材料学院, 天津卤水化工与资源生态化利用重点实验室, 天津 300457
  • 收稿日期:2020-07-02 出版日期:2020-12-10 发布日期:2020-12-09
  • 通讯作者: 陈延辉 E-mail:cyh@tust.edu.cn
  • 基金资助:
    国家自然科学基金(21371131)

Synthesis of Aminophosphine Ruthenium Carbene Complex and Its Application in Olefins Metathesis Reaction

WANG Jinyu, LIU Chunli, CHEN Yanhui()   

  1. Tianjin Key Laboratory of Brine Chemical Engineering and Resource Eco?utilization,College of Chemical Engineering and Materials Science,Tianjin University of Science & Technology,Tianjin 300457,China
  • Received:2020-07-02 Online:2020-12-10 Published:2020-12-09
  • Contact: CHEN Yanhui E-mail:cyh@tust.edu.cn
  • Supported by:
    ? Supported by the National Natural Science Foundation of China(21371131)

摘要:

合成并表征了一类含新型胺基膦配体的Grubbs二代型钌卡宾烯烃复分解催化剂[RuCl2(H2IMes)·(R1HNPR22)(=CHPh)], 采用核磁共振波谱和单晶X射线衍射确定了催化剂的结构. 在室温条件下, 以N,N-二烯丙基-对甲苯磺酰胺的关环复分解反应(RCM)为模型, 考察了不同胺基膦配体对钌卡宾催化反应速率的影响. 结果表明, G2?1表现出最佳的催化活性. 通过底物研究发现, G2?1催化剂(摩尔分数, 1%)对双端烯及多端烯的RCM反应具有较好的活性和官能团适应性, 产物收率均>95%; G2?1催化剂同样适用于同(异)端烯底物的交叉复分解反应(CM), 其催化苯乙烯与3-苯氧基丙烯的CM反应时产物收率高达92%.

关键词: 胺基膦配体, 钌卡宾配合物, 关环复分解, 交叉复分解

Abstract:

A series of Grubbs ruthenium carbene catalysts featuring an aminophosphine ligand [RuCl2·(H2IMes)(R1HNPR22)(=CHPh)] was synthesized and characterized by means of nuclear magnetic resonance spectrometry and single crystal X-ray diffraction. Under the ambient conditions, these ruthenium complexes were tested as catalyst for the ring-closing metathesis(RCM) reaction of N,N-diallyl-p-toluenesulfonamide, and complex G2?1 was found to have the best catalytic activity. With the catalyst loading in the range of 0.1%—2.0%(molar fraction), G2?1 was compatible with the RCM reaction of various diene and polyene, and had high catalytic activity(>95% yield of product). G2?1 could also be used as catalyst for cross metathesis(CM) reaction of different terminal olefin substrates, up to 92% yield was achieved in the CM reaction of styrene and 3-phenoxypropene.

Key words: Aminophosphine, Ruthenium carbene complex, Ring-closing metathesis, Cross metathesis

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