Asymmetric NiH-Catalyzed Regioselective Hydroalkynylation of Unactivated Alkenes  

作　　者：Mengyuan Liu Haoran Shi Xiao Meng Rui He Jie Huang Jiaxin Wang Jun Lv Chao Wang 

机构地区：[1]Tianjin Key Laboratory of Structure and Performance for Functional Molecules,College of Chemistry,Tianjin Normal University,Tianjin 300387

出　　处：《CCS Chemistry》2024年第8期1929-1940,共12页中国化学会会刊（英文）

基　　金：supported by the National Natural Science Foundation of China(grant no.21901185);funds provided by Tianjin Normal University,China.

摘　　要：Herein,we disclose a ligand-controlled,directing group-assisted strategy to facilitate NiH-catalyzed hydroalkynylation of allyl amides at remoteα-position adjacent to nitrogen and initial olefinic site in a predictable and switchable manner.Bromoalkynedependent regiodivergent hydroalkynylation and asymmetric hydroalkynylation with a wide alkyne scope were achieved,producingα-and(enantioenriched)β-branched alkynyl-functionalized amine derivatives from the same raw materials.The formation of a carbonyl-ligated 5-or 6-membered nickelacycle intermediate via Ni migration or nonmigration was believed to be the key step in controlling the regioselectivity.This asymmetric protocol could be applied to synthesizing other value-added chiral aliphatic amines.

关 键 词：asymmetric catalysis hydroalkynylation regiodivergent chain-walking nickel catalysis 

分 类 号：O62[理学—有机化学]