Ligand-controlled NiH-catalyzed regiodivergent hydroalkylation of 2-alkenylazaarenes

作     者：Ya-Ping Shao Zhuo-Min Chi Yong-Min Liang 

作者机构：State Key Laboratory of Applied Organic ChemistrySchool of Chemistry and Chemical EngineeringLanzhou UniversityLanzhou730000China 

出 版 物：《Science China Chemistry》 (中国科学（化学英文版）)

年 卷 期：2024年第67卷第6期

页      面：1935-1940页

核心收录：

学科分类：07[理学] 070303[理学-有机化学] 0703[理学-化学] 

基　　金：supported by the Dalian Institute of Chemical Physics,the Chinese Academy of Sciences the National Natural Science Foundation of China(21472186,21272231)。 

主　　题：NiH regiodivergent hydroalkylation azaarenes interrupted chain-walking 

摘      要：A nickel-hydride(Ni H)-catalyzed migratory and nonmigratory hydroalkylation reaction of 2-alkenyl azaarenes with alkyl iodines has been established through strategic modulation of N-or P-donor ligands.This method enables the synthesis of diverseβ-orγ-branched aromatic N-heterocycles.The mild regiodivergent protocols exhibit wide substrate scope,excellent functional tolerance,and great reaction yield with remarkable regioselectivity.Importantly,deuterium labeling studies reveal Ni H-catalyzed interrupted chain-walking mode as the mechanism behind remotedβ-selective hydroalkylation reaction—an interesting phenomenon mediated through aromatic imine directing groups.