title: Remote C-H Activation of Quinolines through Copper-Catalyzed Radical Cross-Coupling.
abstract: Achieving site selectivity in carbon-hydrogen (C-H) functionalization reactions is a formidable challenge in organic chemistry. Herein, we report a novel approach to activating remote C-H bonds at the C5 position of 8-aminoquinoline through copper-catalyzed sulfonylation under mild conditions. Our strategy shows high conversion efficiency, a broad substrate scope, and good toleration with different functional groups. Furthermore, our mechanistic investigations suggest that a single-electron-transfer process plays a vital role in generating sulfonyl radicals and subsequently initiating C-S cross-coupling. Importantly, our copper-catalyzed remote functionalization protocol can be expanded for the construction of a variety of chemical bonds, including C-O, C-Br, C-N, C-C, and C-I. These findings provide a fundamental insight into the activation of remote C-H bonds, while offering new possibilities for rational design of drug molecules and optoelectronic materials requiring specific modification of functional groups.
authors.affiliation: College of Material, Chemistry and Chemical Engineering, Hangzhou Normal University, Hangzhou, 310036, China.
authors.forename: Jun
authors.initials: J
authors.lastname: Xu
authors.affiliation: College of Biology and Environmental Engineering, Zhejiang Shuren University, Hangzhou, China.
authors.forename: Chao
authors.initials: C
authors.lastname: Shen
authors.affiliation: College of Material, Chemistry and Chemical Engineering, Hangzhou Normal University, Hangzhou, 310036, China.
authors.forename: Xiaolei
authors.initials: X
authors.lastname: Zhu
authors.affiliation: College of Material, Chemistry and Chemical Engineering, Hangzhou Normal University, Hangzhou, 310036, China. chxyzpf@hotmail.com.
authors.forename: Pengfei
authors.initials: P
authors.lastname: Zhang
authors.affiliation: KAUST Catalysis Center and Division of Physical Science and Engineering, King Abdullah University of Science and Technology, Thuwal, 23955-6900, Saudi Arabia.
authors.forename: Manjaly J
authors.initials: MJ
authors.lastname: Ajitha
authors.affiliation: KAUST Catalysis Center and Division of Physical Science and Engineering, King Abdullah University of Science and Technology, Thuwal, 23955-6900, Saudi Arabia. hkw@kaust.edu.sa.
authors.forename: Kuo-Wei
authors.initials: KW
authors.lastname: Huang
authors.affiliation: Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore, 117543, Singapore.
authors.forename: Zhongfu
authors.initials: Z
authors.lastname: An
authors.affiliation: Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore, 117543, Singapore. chmlx@nus.edu.sg.
authors.forename: Xiaogang
authors.identifier: http://orcid.org/0000-0003-2517-5790
authors.initials: X
authors.lastname: Liu
mesh_terms: D002384:Catalysis; D003300:Copper / Q000737:chemistry*; D011804:Quinolines / Q000737:chemistry*
chemical_list: D011804:Quinolines; D003300:Copper
keywords: cross-coupling; radicals; remote C−H functionalization; sulfonylation