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

被引:92
作者
Hamilton, Robin J. [1 ]
Bergens, Steven H. [1 ]
机构
[1] Univ Alberta, Dept Chem, Edmonton, AB T6G 2G2, Canada
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
收藏
页码:11979 / 11987
页数:9
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共 41 条
[21]   Realistic modeling of ruthenium-catalyzed transfer hydrogenation [J].
Handgraaf, Jan-Willem ;
Meijer, Evert Jan .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2007, 129 (11) :3099-3103
[22]   Iridium(I) versus ruthenium(II). A computational study of the transition metal catalyzed transfer hydrogenation of ketones [J].
Handgraaf, JW ;
Reek, JNH ;
Meijer, EJ .
ORGANOMETALLICS, 2003, 22 (15) :3150-3157
[23]   Mechanistic insights into the phosphine-free RuCp☆-diamine-catalyzed hydrogenation of aryl ketones:: Experimental and theoretical evidence for an alcohol-mediated dihydrogen activation [J].
Hedberg, C ;
Källström, K ;
Arvidsson, PI ;
Brandt, P ;
Andersson, PG .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2005, 127 (43) :15083-15090
[24]   Asymmetric transfer hydrogenation of ketones with bifunctional transition metal-based molecular [J].
Ikariya, Takao ;
Blacker, A. John .
ACCOUNTS OF CHEMICAL RESEARCH, 2007, 40 (12) :1300-1308
[25]   Catalytic hydrogenation of polar organic functionalities based on Ru-mediated heterolytic dihydrogen cleavage [J].
Ito, Masato ;
Ikariya, Takao .
CHEMICAL COMMUNICATIONS, 2007, (48) :5134-5142
[26]   Mechanism of ruthenium-catalyzed hydrogen transfer reactions.: Concerted transfer of OH and CH hydrogens from an alcohol to a (cyclopentadienone)ruthenium complex [J].
Johnson, JB ;
Bäckvall, JE .
JOURNAL OF ORGANIC CHEMISTRY, 2003, 68 (20) :7681-7684
[27]   Origin of enantioselective hydrogenation of ketones by RuH2(diphosphine)(diamine) catalysts:: A theoretical study [J].
Leyssens, Tom ;
Peeters, Daniel ;
Harvey, Jeremy N. .
ORGANOMETALLICS, 2008, 27 (07) :1514-1523
[28]   Bifunctional metal-ligand catalysis:: Hydrogenations and new reactions within the metal-(di)amine scaffold [J].
Muñiz, K .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2005, 44 (41) :6622-6627
[29]   Metal-ligand bifunctional catalysis for asymmetric hydrogenation [J].
Noyori, R ;
Sandoval, CA ;
Muniz, K ;
Ohkuma, T .
PHILOSOPHICAL TRANSACTIONS OF THE ROYAL SOCIETY A-MATHEMATICAL PHYSICAL AND ENGINEERING SCIENCES, 2005, 363 (1829) :901-912
[30]   Toward efficient asymmetric hydrogenation: Architectural and functional engineering of chiral molecular catalysts [J].
Noyori, R ;
Kitamura, M ;
Ohkuma, T .
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA, 2004, 101 (15) :5356-5362