A Multilateral Mechanistic Study into Asymmetric Transfer Hydrogenation in Water

作者: Xiaofeng Wu , Jianke Liu , Devis Di Tommaso , Jonathan A. Iggo , C. Richard A. Catlow

DOI: 10.1002/CHEM.200800559

关键词: Transfer hydrogenationCatalytic cycleChemistryAcetophenoneRutheniumKetoneEnantioselective synthesisHydridePhotochemistryCatalysisMedicinal chemistry

摘要: The mechanism of aqueous‐phase asymmetric transfer hydrogenation (ATH) of acetophenone (acp) with HCOONa catalyzed by Ru‐TsDPEN has been investigated by stoichiometric reactions, NMR probing, kinetic and isotope effect measurements, DFT modeling, and X‐ray structure analysis. The chloride [RuCl (TsDPEN)(p‐cymene)](1), hydride [RuH (TsDPEN)(p‐cymene)](3), and the 16‐electorn species [Ru (TsDPEN‐H)(p‐cymene)](4) were shown to be involved in the aqueous ATH, with 1 being the precatalyst …

参考文章(189)
R. Noyori, M. Kitamura, T. Ohkuma, Toward efficient asymmetric hydrogenation: Architectural and functional engineering of chiral molecular catalysts Proceedings of the National Academy of Sciences of the United States of America. ,vol. 101, pp. 5356- 5362 ,(2004) , 10.1073/PNAS.0307928100
Alessandro Ponti, Giorgio Molteni, Uncommon aqueous media for nitrilimine cycloadditions. II. Computational study of the effect of water on reaction rate New Journal of Chemistry. ,vol. 26, pp. 1346- 1351 ,(2002) , 10.1039/B205071D
Hae Yoon Rhyoo, Hee-Jung Park, Young Keun Chung, The first Ru(II)-catalysed asymmetric hydrogen transfer reduction of aromatic ketones in aqueous media Chemical Communications. pp. 2064- 2065 ,(2001) , 10.1039/B106130P
Takao Ikariya, A. John Blacker, Asymmetric transfer hydrogenation of ketones with bifunctional transition metal-based molecular catalysts. Accounts of Chemical Research. ,vol. 40, pp. 1300- 1308 ,(2007) , 10.1021/AR700134Q
A.W. Ehlers, M. Böhme, S. Dapprich, A. Gobbi, A. Höllwarth, V. Jonas, K.F. Köhler, R. Stegmann, A. Veldkamp, G. Frenking, A set of f-polarization functions for pseudo-potential basis sets of the transition metals ScCu, YAg and LaAu Chemical Physics Letters. ,vol. 208, pp. 111- 114 ,(1993) , 10.1016/0009-2614(93)80086-5
Jérˆome Canivet, Bruno Therrien, Georg Süss-Fink, None, [(R,R)-2-Amino-1-(p-tolylsulfonylamido)cyclohexane-κ2N,N']chloro(η5-pentamethylcyclopentadienyl)iridium(III) chloroform solvate Acta Crystallographica Section E-structure Reports Online. ,vol. 62, ,(2006) , 10.1107/S1600536806034842