ENANTIOSELECTIVE HYDROGENATION OF ETHYL PYRUVATE - INFLUENCE OF OXIDATIVE TREATMENT OF CINCHONIDINE-MODIFIED PLATINUM CATALYST AND HEMIKETAL FORMATION IN ALCOHOLIC SOLVENTS

被引：73

作者：

MINDER, B ^{[1
]}

MALLAT, T ^{[1
]}

SKRABAL, P ^{[1
]}

BAIKER, A ^{[1
]}

机构：

[1] SWISS FED INST TECHNOL,SWISS FED INST TECHNOL,INST POLYMERS,CH-8092 ZURICH,SWITZERLAND

来源：

CATALYSIS LETTERS | 1994年 / 29卷 / 1-2期

关键词：

ENANTIOSELECTIVE HYDROGENATION; PT-ALUMINA; CINCHONIDINE; ETHYL PYRUVATE; PROTONATION; HEMIKETAL FORMATION;

D O I：

10.1007/BF00814258

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

The reasons for the increase in the rate and enantiomeric excess after oxidative (aerobic) treatment of Pt/alumina in ethanol have been investigated. It is demonstrated that their treatment results in the formation of acetic acid and consequently in the protonation of the quinuclidine N1 of cinchonidine. This favours the cinchonidine-pyruvate interaction and improves enantioselectivity. In addition, the reaction rate is enhanced due to acid catalysis of the carbonyl. reduction. NMR and UV measurements indicate the rapid transformation of ethyl pyruvate to the corresponding hemiketal in primary alcohols as solvents. It is shown that the possible involvement of this hemiketal (and that formed between cinchonidine and ethyl pyruvate) as an intermediate in the pyruvate hydrogenation mechanism can be excluded.

引用

页码：115 / 124

页数：10

共 45 条

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Margitfalvi, J. L.
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Tfirst, E.
TOPICS IN CATALYSIS, 2006, 39 (1-2) : 77 - 87
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J. L. Margitfalvi
E. Tálas
E. Tfirst
Topics in Catalysis, 2006, 39 : 77 - 87
[33] Hydrogen Deuterium Isotopic Labeling Study of Enantioselective Hydrogenation of (E)-2-Methyl-2-butenoic Acid over a Cinchonidine-Modified Pd/C Catalyst
Sugimura, Takashi
Tomatsuri, Satoshi
Fujita, Morifumi
Okamoto, Yasuaki
BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN, 2019, 92 (10) : 1737 - 1742
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Kraynov, A.
Richards, R.
APPLIED CATALYSIS A-GENERAL, 2006, 314 (01) : 1 - 8
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Imre Bucsi
György Szöllősi
Tibor Bartók
Mihály Bartók
Reaction Kinetics and Catalysis Letters, 2005, 85 : 361 - 366
[36] Kinetic studies of the enantioselective hydrogenation of ethyl pyruvate catalyzed by a cinchona modified Pt/Al2O3 catalyst
Blaser, HU
Jalett, HP
Garland, M
Studer, M
Thies, H
Wirth-Tijani, A
JOURNAL OF CATALYSIS, 1998, 173 (02) : 282 - 294
[37] Kinetic Studies of the Enantioselective Hydrogenation of Ethyl Pyruvate Catalyzed by a Cinchona Modified Pt/Al2O3 Catalyst
Blaser, H.-U.
Jalett, H.-P.
Garland, M.
Studer, M.
Journal of Catalysis, 173 (02):
[38] A new cinchona-modified platinum catalyst for the enantioselective hydrogenation of pyruvate:: the structure of the 1:1 alkaloid-reactant complex
Bartók, M
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Török, B
Bartók, T
CHEMICAL COMMUNICATIONS, 1998, (23) : 2605 - 2606
[39] A kinetic probe of the effect of a stabilizing polymer on a colloidal catalyst: Accelerated enantioselective hydrogenation of ethyl pyruvate catalyzed by poly(vinylpyrrolidone)-stabilized platinum colloids
Kohler, JU
Bradley, JS
LANGMUIR, 1998, 14 (10) : 2730 - 2735
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Szöllösi, G
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Szabó, PT
Bartók, M
JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL, 2001, 170 (1-2) : 165 - 173

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