Highly Enantioselective Hydrogenation of Quinolines Using Phosphine-Free   Chiral Cationic Ruthenium Catalysts: Scope, Mechanism, and Origin of   Enantioselectivity

doi:10.1021/ja2023042

CORC > 北京大学 > 化学与分子工程学院

	Highly Enantioselective Hydrogenation of Quinolines Using Phosphine-Free Chiral Cationic Ruthenium Catalysts: Scope, Mechanism, and Origin of Enantioselectivity
	Wang, Tianli ; Zhuo, Lian-Gang ; Li, Zhiwei ; Chen, Fei ; Ding, Ziyuan ; He, Yanmei ; Fan, Qing-Hua ; Xiang, Junfeng ; Yu, Zhi-Xiang ; Chan, Albert S. C.
刊名	journal of the american chemical society
	2011
关键词	ASYMMETRIC TRANSFER HYDROGENATION LIGAND BIFUNCTIONAL CATALYSIS 3+2 CYCLOADDITION REACTIONS TRANSFER PROTEIN INHIBITOR AROMATIC KETONES HETEROAROMATIC-COMPOUNDS GALIPEA-OFFICINALIS CARBONYL-COMPOUNDS IRIDIUM COMPLEXES COOPERATIVE CATALYSIS
DOI	10.1021/ja2023042
英文摘要	Asymmetric hydrogenation of quinolines catalyzed by chiral cationic eta(6)-arene N-tosylethylenediamine-Ru(II) complexes have been investigated. A wide range of quinoline derivatives, including 2-alkylquinolines, 2-arylquinolines, and 2-functionalized and 2,3-disubstituted quinoline derivatives, were efficiently hydrogenated to give 1,2,3,4-tetra-hydroquinolines with up to >99% ee and full conversions. Thiscatalytic protocol is applicable to the gram-scale synthesis of some biologically active tetrahydroquinolines, such as (-)-angustureine, and 6-fluoro-2-methyl-1,2,3,4-tetrahydroquinoline, a key intermediate for the preparation of the antibacterial agent (S)-flumequine. The catalytic pathway of this reaction has been investigated in detail using a combination of stoichiometric reaction, intermediate characterization, and isotope labeling patterns. The evidence obtained from these experiments revealed that quinoline is reduced via an ionic and cascade reaction pathway, including 1,4-hydride addition, isomerization, and 1,2-hydride addition, and hydrogen addition undergoes a stepwise H+/H- transfer process outside the coordination sphere rather than a concerted mechanism. In addition, DFT calculations indicate that the enantioselectivity originates from the CH/pi attraction between the eta(6)-arene ligand in the Ru-complex and the fused phenyl ring of dihydroquinoline via a 10-membered ring transition state with the participation of TfO- anion.; Chemistry, Multidisciplinary; SCI(E); EI; 116; ARTICLE; 25; 9878-9891; 133
语种	英语
内容类型	期刊论文
源URL	[http://ir.pku.edu.cn/handle/20.500.11897/239502]
专题	化学与分子工程学院
推荐引用方式 GB/T 7714	Wang, Tianli,Zhuo, Lian-Gang,Li, Zhiwei,et al. Highly Enantioselective Hydrogenation of Quinolines Using Phosphine-Free Chiral Cationic Ruthenium Catalysts: Scope, Mechanism, and Origin of Enantioselectivity[J]. journal of the american chemical society,2011.
APA	Wang, Tianli.,Zhuo, Lian-Gang.,Li, Zhiwei.,Chen, Fei.,Ding, Ziyuan.,...&Chan, Albert S. C..(2011).Highly Enantioselective Hydrogenation of Quinolines Using Phosphine-Free Chiral Cationic Ruthenium Catalysts: Scope, Mechanism, and Origin of Enantioselectivity.journal of the american chemical society.
MLA	Wang, Tianli,et al."Highly Enantioselective Hydrogenation of Quinolines Using Phosphine-Free Chiral Cationic Ruthenium Catalysts: Scope, Mechanism, and Origin of Enantioselectivity".journal of the american chemical society (2011).