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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Dummer, NF
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CATALYSIS IN APPLICATION, 2003, : 278 - 283
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T. Mallat
M. Bodmer
A. Baiker
Catalysis Letters, 1997, 44 : 95 - 99
[3] Enantioselective hydrogenation of trifluoroacetophenone over cinchonidine-modified platinum
Mallat, T
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Balker, A
CATALYSIS LETTERS, 1997, 44 (1-2) : 95 - 99
[4] Enantioselective hydrogenation of β-dehydroamino acids on a cinchonidine-modified palladium catalyst
Chen, Chunhui
Zhan, Ensheng
Li, Yong
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JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL, 2013, 379 : 117 - 121
[5] On the implications of hemiketal formation during ethyl pyruvate hydrogenation in alcohol solvents
Bohnen, FM
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Blackmond, DG
JOURNAL OF CATALYSIS, 1998, 179 (02) : 335 - 338
[6] Enantioselective hydrogenation of (E)-α-phenylcinnamic acid with cinchonidine-modified Pd/TiO2: influence of solvents and additives
Yuriko Nitta
Topics in Catalysis, 2000, 13 : 179 - 185
[7] Induction period for the enantioselective hydrogenation of α,β-unsaturated acids over a cinchonidine-modified palladium catalyst
Takuya Mameda
Tomonori Misaki
Yasuaki Okamoto
Takashi Sugimura
Reaction Kinetics, Mechanisms and Catalysis, 2015, 114 : 55 - 61
[8] Induction period for the enantioselective hydrogenation of α,β-unsaturated acids over a cinchonidine-modified palladium catalyst
Mameda, Takuya
Misaki, Tomonori
Okamoto, Yasuaki
Sugimura, Takashi
REACTION KINETICS MECHANISMS AND CATALYSIS, 2015, 114 (01) : 55 - 61
[9] Enantioselective hydrogenation of (E)-α-phenylcinnamic acid with cinchonidine-modified Pd/TiO2:: influence of solvents and additives
Nitta, Y
TOPICS IN CATALYSIS, 2000, 13 (03) : 179 - 185
[10] ENANTIOSELECTIVE HYDROGENATION .1. SURFACE CONDITIONS DURING METHYL PYRUVATE HYDROGENATION CATALYZED BY CINCHONIDINE-MODIFIED PLATINUM SILICA (EUROPT-1)
SUTHERLAND, IM
IBBOTSON, A
MOYES, RB
WELLS, PB
JOURNAL OF CATALYSIS, 1990, 125 (01) : 77 - 88

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