胺基膦钌卡宾化合物的合成及催化烯烃复分解反应  

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

作　　者：王晋宇 柳春丽 陈延辉 WANG Jinyu;LIU Chunli;CHEN Yanhui(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)

机构地区：[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

出　　处：《高等学校化学学报》2020年第12期2766-2773,共8页Chemical Journal of Chinese Universities

基　　金：国家自然科学基金(批准号:21371131)资助.

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%.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.

关 键 词：胺基膦配体 钌卡宾配合物 关环复分解 交叉复分解 

分 类 号：O621.2[理学—有机化学]