ICCAS OpenIR
Highly Enantioselective Hydrogenation of Quinolines Using Phosphine-Free Chiral Cationic Ruthenium Catalysts: Scope, Mechanism, and Origin of Enantioselectivity
Wang, Tianli1,2; Zhuo, Lian-Gang3; Li, Zhiwei1,2; Chen, Fei1,2; Ding, Ziyuan1,2; He, Yanmei1,2; Fan, Qing-Hua1,2; Xiang, Junfeng1,2; Yu, Zhi-Xiang3; Chan, Albert S. C.4
2011-06-29
Source PublicationJOURNAL OF THE AMERICAN CHEMICAL SOCIETY
ISSN0002-7863
Volume133Issue:25Pages:9878-9891
AbstractAsymmetric 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.
DOI10.1021/ja2023042
Indexed BySCI ; IC ; CCR
Language英语
WOS IDWOS:000292439700044
PublisherAMER CHEMICAL SOC
Citation statistics
Cited Times:221[WOS]   [WOS Record]     [Related Records in WOS]
Document Type期刊论文
Identifierhttp://ir.iccas.ac.cn/handle/121111/71448
Collection中国科学院化学研究所
Corresponding AuthorFan, Qing-Hua
Affiliation1.Chinese Acad Sci, Beijing Natl Lab Mol Sci, CAS Key Lab Mol Recognit & Funct, Inst Chem, Beijing 100190, Peoples R China
2.Chinese Acad Sci, Grad Sch, Beijing 100190, Peoples R China
3.Peking Univ, Coll Chem, Minist Educ, Key Lab Bioorgan Chem & Mol Engn, Beijing 100871, Peoples R China
4.Hong Kong Baptist Univ, Inst Creat, Hong Kong, Hong Kong, Peoples R China
Recommended Citation
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,2011,133(25):9878-9891.
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,133(25),9878-9891.
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 133.25(2011):9878-9891.
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