Base-Catalyzed Bifunctional Addition to Amides and Imides at Low Temperature. A New Pathway for Carbonyl Hydrogenation

被引：70

作者：

John, Jeremy M. ^{[1
]}

Takebayashi, Satoshi ^{[1
]}

Dabral, Nupur ^{[1
]}

Miskolzie, Mark ^{[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 | 2013年 / 135卷 / 23期

关键词：

HYDROXYCYCLOPENTADIENYL RUTHENIUM HYDRIDE; ASYMMETRIC HYDROGENATION; ENANTIOSELECTIVE HYDROGENATION; AROMATIC KETONES; PROTON-TRANSFER; COMPLEXES; MECHANISM; REDUCTION; IMINES; ALCOHOLS;

D O I：

10.1021/ja401294q

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Mono- or dideprotonation at the N-H groups of the Noyori ketone hydrogenation catalyst trans-[RuH2((R)-BINAP)((R,R)-dpen)] (1a) yields trans-M[RuH2((R,R)HNCH(Ph)CH(Ph)NH2)((R)-BINAP)], where M = K+ (8-K) or Li+ (8-Li), or trans-M-2[RuH2((R,R)-HNCH(Ph)-CH(Ph)NH)((R)-BINAP)], where M = Li+ (8-M-2'), which have unprecedented activity toward the hydrogenation of amide and imide carbonyls at low temperatures in THF-d(8). Details of the origins of the enantioselection for the desymmetrization of meso-cyclic imides by hydrogenation with 8-K are also described herein.

引用

页码：8578 / 8584

页数：7

共 82 条

[31] New insights into the enantioselectivity in the hydrogenation of prochiral ketones
French, Samuel A.
Di Tommaso, Devis
Zanotti-Gerosa, Antonio
Hancock, Fred
Catlow, C. Richard A.
[J]. CHEMICAL COMMUNICATIONS, 2007, (23) : 2381 - 2383
[32] A comprehensive investigation of the chemistry and basicity of a parent amidoruthenium complex
Fulton, JR
Sklenak, S
Bouwkamp, MW
Bergman, RG
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2002, 124 (17) : 4722 - 4737
[33] Gribble GW, 1998, CHEM SOC REV, V27, P395
[34] A mechanism displaying autocatalysis:: The hydrogenation of acetophenone catalyzed by RuH(S-binap)(app) where app is the amido ligand derived from 2-amino-2-(2-pyridyl)propane
Hadzovic, Alen
Song, Datong
MacLaughlin, Christina M.
Morris, Robert H.
[J]. ORGANOMETALLICS, 2007, 26 (24) : 5987 - 5999
[35] A ruthenium-dihydrogen putative intermediate in ketone hydrogenation
Hamilton, RJ
Leong, CG
Bigam, G
Miskolzie, M
Bergens, SH
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2005, 127 (12) : 4152 - 4153
[36] Direct observations of the metal-ligand bifunctional addition step in an enantioselective ketone hydrogenation
Hamilton, Robin J.
Bergens, Steven H.
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2008, 130 (36) : 11979 - 11987
[37] An unexpected possible role of base in asymmetric catalytic hydrogenations of ketones. Synthesis and characterization of several key catalytic intermediates
Hamilton, Robin J.
Bergens, Steven H.
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2006, 128 (42) : 13700 - 13701
[38] Numerical modeling of differential kinetics in the asymmetric hydrogenation of acetophenone by Noyori's catalyst
Hartmann, R
Chen, P
[J]. ADVANCED SYNTHESIS & CATALYSIS, 2003, 345 (12) : 1353 - 1359
[39] Hartmann R, 2001, ANGEW CHEM INT EDIT, V40, P3581, DOI 10.1002/1521-3773(20011001)40:19<3581::AID-ANIE3581>3.0.CO
[40] 2-7

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