过渡金属铑催化的环状亚胺与炔烃的[3+2]环合反应的研究

Rhodium-Catalyzed [3+2] Annulations of Cyclic Ketimines and Alkynes

在过渡金属铑催化作用下,3-苯基-2H-苯并[b][1,4]噁嗪类环状亚胺为底物与二苯基乙炔进行[3+2]环合反应,实现了五元碳环的构筑从而获得了多环状的茚基骨架的手性胺。考察了反应溶剂、添加剂种类、反应时间、反应温度及芳烃结构对反应的影响,确定了最佳的反应条件:0.24 mmol二苯基乙炔与0.2 mmol环状亚胺反应,在[Cp*RhCl2]2(2.5 mol%)、醋酸铜(20 mol%)作用下,反应温度为50℃,时间为12 h。在此反应条件下,富电子的芳烃反应较好,缺电子的芳烃反应相对较差,富电子的炔类物质产率略低。

A rhodium-catalyzed[3+2]annulations reaction of 3-phenyl-2H-benzo[b][1,4]oxazine ring imine substrates and 1,2-disubstituted acetylene was realized and a five-membered carbon ring structure was successfully constructed to form a pericyclic indenyl amine.The effects of solvent,additive,reaction time,reaction temperature and the structure of arene on the reaction were investigated.The optimal reaction conditions were as follows:0.24 mmol of diphenylacetylene,0.2 mmol of cyclic imine in the presence of[Cp*RhCl2]2(2.5 mol%)and copper acetate(20 mol%)at 50℃for 12 h.Under these conditions,the electron rich arenes react more effectively than the electron deficient arenes,and the electron rich acetylenes yields slightly lower.