title: Titanium-mediated reductive cross-coupling reactions of imines with terminal alkynes: An efficient route for the synthesis of stereodefined allylic amines.
abstract: 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.
authors.affiliation: 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 ; College of Chemical Engineering, Shenyang University of Chemical Technology, Shenyang 110142, People's Republic of China.
authors.forename: Kebin
authors.initials: K
authors.lastname: Mao
authors.forename: Guoqin
authors.initials: G
authors.lastname: Fan
authors.forename: Yuanhong
authors.initials: Y
authors.lastname: Liu
authors.forename: Shi
authors.initials: S
authors.lastname: Li
authors.forename: Xu
authors.initials: X
authors.lastname: You
authors.forename: Dan
authors.initials: D
authors.lastname: Liu
keywords: allylic amine; azatitanacyclopentene; reductive cross-coupling; regioselectivity; terminal alkyne; titanium-imine complex