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

[41] Heterogeneous asymmetric reactions. 23. Enantioselective hydrogenation of ethyl pyruvate over cinchonine- and α-isocinchonine-modified platinum catalysts
Mihály Bartók
Béla Török
Katalin Balázsik
Tibor Bartók
Catalysis Letters, 2001, 73 : 127 - 131
[42] Heterogeneous asymmetric reactions.: 23.: Enantioselective hydrogenation of ethyl pyruvate over cinchonine- and α-isocinchonine-modified platinum catalysts
Bartók, M
Török, B
Balázsik, K
Bartók, T
CATALYSIS LETTERS, 2001, 73 (2-4) : 127 - 131
[43] Heterogeneous Asymmetric Reactions. 29. Enantioselective Hydrogenation of Ethyl Benzoylformate over Dihydrocinchonidine-Modified Platinum–Alumina Catalyst in Acetic Acid
Mária Sutyinszki
Kornél Szöri
Károly Felföldi
Mihály Bartók
Catalysis Letters, 2002, 81 : 281 - 284
[44] Identification of novel chiral aluminium containing oxonium cations in the enantioselective hydrogenation of ethyl pyruvate catalyzed using cinchonidine modified Pt-alumina in acetic acid (vol 85, pg 361, 2005)
Bucsi, I
Szöllösi, G
Bartók, T
Bartók, M
REACTION KINETICS AND CATALYSIS LETTERS, 2005, 86 (01): : 217 - 217
[45] Heterogeneous asymmetric reactions.: 29.: Enantioselective hydrogenation of ethyl benzoylformate over dihydrocinchonidine-modified platinum-alumina catalyst in acetic acid
Sutyinszki, M
Szöri, K
Felföldi, K
Bartók, M
CATALYSIS LETTERS, 2002, 81 (3-4) : 281 - 284

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