Titanium-mediated reductive cross-coupling reactions of imines with terminal alkynes: An efficient route for the synthesis of stereodefined allylic amines

Beilstein Journal of Organic Chemistry

Dan Liu¹  Xu You²  Yuanhong Liu²  Shi Li²  Guoqin Fan²  Kebin Mao² 

[1] College of Chemical Engineering, Shenyang University of Chemical Technology, Shenyang 110142, People’s Republic of China;State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Lu, Shanghai 200032, People’s Republic of China;

关键词: allylic amine;    azatitanacyclopentene;    reductive cross-coupling;    regioselectivity;    terminal alkyne;    titanium-imine complex;   

DOI  :  10.3762/bjoc.9.69

来源: DOAJ

【 摘 要 】

Low-valency titanium species, generated in situ by using Ti(OiPr)4/2 c-C5H9MgCl reagent, react with imines to give a titanium-imine complex that can couple with terminal alkynes to provide azatitanacyclopentenes with excellent regioselectivity. Stereodefined allylic amines are obtained in good yields after hydrolysis or iodonolysis of the corresponding azatitanacyclopentenes. When ethynylcyclopropane is used as the coupling partner to react with imines in this reaction, the initially generated allylic amine undergoes an unexpected 1,3-amino migration on silica gel during the column chromatography.

【 授权许可】

Unknown