Direct observations of the metal-ligand bifunctional addition step in an enantioselective ketone hydrogenation

被引：91

作者：

Hamilton, Robin J. ^{[1
]}

Bergens, Steven H. ^{[1
]}

机构：

[1] Univ Alberta, Dept Chem, Edmonton, AB T6G 2G2, Canada

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2008年 / 130卷 / 36期

基金：

加拿大自然科学与工程研究理事会;

关键词：

D O I：

10.1021/ja8034812

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The catalytic intermediate trans-[Ru((R)-BINAP)(H)(2)((R,R)-dpen)] (1) reacted on mixing with acetophenone in THF at -80 degrees C under similar to 2 atm H-2 to generate the alkoxide trans-Ru((R)-BINAP)(H)-((Ph)(Me)CHO)((R,R)-dpen) (6). Contrary to expectations, free Ru-amide and 1-phenylethanol were not the immediate products of this addition reaction. The addition reaction was reversible in THF. 2-Propanol prevents racemization of the alcohol product in THF solvent.

引用

页码：11979 / 11987

页数：9

共 41 条

[1] A succession of isomers of ruthenium dihydride complexes. Which one is the ketone hydrogenation catalyst?
Abbel, R
Abdur-Rashid, K
Faatz, M
Hadzovic, A
Lough, AJ
Morris, RH
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2005, 127 (06) : 1870 - 1882
[2] Mechanism of the hydrogenation of ketones catalyzed by trans-dihydrido(diamine)ruthenium(II) complexes
Abdur-Rashid, K
Clapham, SE
Hadzovic, A
Harvey, JN
Lough, AJ
Morris, RH
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2002, 124 (50) : 15104 - 15118
[3] Catalytic cycle for the asymmetric hydrogenation of prochiral ketones to chiral alcohols:: Direct hydride and proton transfer from chiral catalysts trans-Ru(H)2(diphosphine)(diamine) to ketones and direct addition of dihydrogen to the resulting hydridoamido complexes
Abdur-Rashid, K
Faatz, M
Lough, AJ
Morris, RH
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2001, 123 (30) : 7473 - 7474
[4] Mechanistic investigation on the hydrogenation of imines by [p-(Me2CH)C6H4Me]RuH(NH2CHPhCHPhNSO2C6H4-p-CH3).: Experimental support for an ionic pathway
Aberg, Jenny B.
Samec, Joseph S. M.
Baeckvall, Jan-E.
[J]. CHEMICAL COMMUNICATIONS, 2006, (26) : 2771 - 2773
[5] [Anonymous], 2007, HDB HOMOGENEOUS HYDR
[6] Ruthenium(II) terdentate CNN complexes: Superlative catalysts for the hydrogen-transfer reduction of ketones by reversible insertion of a carbonyl group into the Ru-H bond
Baratta, W
Chelucci, G
Gladiali, S
Siega, K
Toniutti, M
Zanette, M
Zangrando, E
Rigo, P
[J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2005, 44 (38) : 6214 - 6219
[7] Catalytic transfer hydrogenation with terdentate CNN ruthenium complexes: The influence of the base
Baratta, Walter
Siega, Katia
Rigo, Pierluigi
[J]. CHEMISTRY-A EUROPEAN JOURNAL, 2007, 13 (26) : 7479 - 7486
[8] Spectroscopic determination of hydrogenation rates and intermediates during carbonyl hydrogenation catalyzed by Shvo's hydroxycyclopentadienyl diruthenium hydride agrees with kinetic modeling based on independently measured rates of elementary reactions
Casey, Charles P.
Beetner, Sharon E.
Johnson, Jeffrey B.
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2008, 130 (07) : 2285 - 2295
[9] Intramolecular trapping of an intermediate in the reduction of Imines by a hydroxycyclopentadienyl ruthenium hydride: Support for a concerted outer sphere mechanism
Casey, Charles P.
Clark, Timothy B.
Guzei, Ilia A.
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2007, 129 (38) : 11821 - 11827
[10] Stereochemistry of imine reduction by a hydroxycyclopentadienyl ruthenium hydride
Casey, CP
Bikzhanova, GA
Guzei, IA
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2006, 128 (07) : 2286 - 2293

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