Remote C−H Activation of Quinolines through Copper-Catalyzed Radical Cross-Coupling
Ajitha, Manjaly John
KAUST DepartmentChemical Science Program
Homogeneous Catalysis Laboratory (HCL)
KAUST Catalysis Center (KCC)
Physical Science and Engineering (PSE) Division
Online Publication Date2016-02-04
Print Publication Date2016-03-18
Permanent link to this recordhttp://hdl.handle.net/10754/621709
MetadataShow full item record
AbstractAchieving 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. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
CitationXu J, Shen C, Zhu X, Zhang P, Ajitha MJ, et al. (2016) Remote C−H Activation of Quinolines through Copper-Catalyzed Radical Cross-Coupling. Chemistry - An Asian Journal 11: 882–892. Available: http://dx.doi.org/10.1002/asia.201501407.
SponsorsWe thank the funding support from the National Natural Science Foundation of China (No. 21376058, 21302171), Zhejiang Provincial Natural Science Foundation of China (No. LZ13B 020001) and the Key-Sci-Tech Innovation Team of Zhejiang Province (No. 2010R50017).
JournalChemistry - An Asian Journal
RelationsIs Supplemented By:
Xu, J., Shen, C., Zhu, X., Zhang, P., Ajitha, M. J., Huang, K.-W., … Liu, X. (2016). CCDC 1041995: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/ccdc.csd.cc13z8r3. DOI: 10.5517/ccdc.csd.cc13z8r3 HANDLE: 10754/624496
Xu, J., Shen, C., Zhu, X., Zhang, P., Ajitha, M. J., Huang, K.-W., … Liu, X. (2016). CCDC 1429311: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/ccdc.csd.cc1jz9tm. DOI: 10.5517/ccdc.csd.cc1jz9tm HANDLE: 10754/624525
- Sulfonylation of quinoline N-oxides with aryl sulfonyl chlorides via copper-catalyzed C-H bonds activation.
- Authors: Wu Z, Song H, Cui X, Pi C, Du W, Wu Y
- Issue date: 2013 Mar 15
- Direct functionalization processes: a journey from palladium to copper to iron to nickel to metal-free coupling reactions.
- Authors: Mousseau JJ, Charette AB
- Issue date: 2013 Feb 19
- Copper-Catalyzed Arylation of Remote C(sp(3) )-H Bonds in Carboxamides and Sulfonamides.
- Authors: Li Z, Wang Q, Zhu J
- Issue date: 2018 Oct 1
- An efficient synthesis of quinolines via copper-catalyzed C-N cleavage.
- Authors: Xi LY, Zhang RY, Zhang L, Chen SY, Yu XQ
- Issue date: 2015 Apr 7
- Substituent-guided switch between C-H activation and decarboxylative cross-coupling during palladium/copper-catalyzed cascade reactions of 2-aminobenzoates with 2-haloarylaldehydes.
- Authors: Bhowmik S, Pandey G, Batra S
- Issue date: 2013 Aug 5