Origin of enhanced rate in the platinum-catalysed enantioselective hydrogenation of methyl pyruvate

Bond, G. C.; Meheux, P.A.; Ibbotson, A.; Wells, Peter B.

doi:10.1016/0920-5861(91)80018-5

Cited by 67 publications

(26 citation statements)

References 4 publications

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“…Upon using a-ICN the lack of RA is highly anomalous as it is known that achiral tertiary amines, such as quinuclidine, DABCO, trimethylamine, etc., induce pronounced RA, but without ED [35]. The RA caused by tertiary amines was interpreted in term of nucleophilic attack of the tertiary nitrogen atom to the carbon atom of the keto group [17,[36][37][38].…”

Section: Kinetic Resultsmentioning

confidence: 99%

Anomalous behavior of rigid cinchona alkaloids in the enantioselective hydrogenation of ethyl pyruvate in an aprotic solvent

Margitfalvi

Tálas

2006

Applied Catalysis A: General

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Section: Kinetic Resultsmentioning

confidence: 99%

Anomalous behavior of rigid cinchona alkaloids in the enantioselective hydrogenation of ethyl pyruvate in an aprotic solvent

Margitfalvi

Tálas

2006

Applied Catalysis A: General

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“…These values allow to differentiate between enantioselective and the racemic hydrogenations. These two terms reflect the rate acceleration phenomenon observed by most of the research groups [2,8,11,23,24].…”

Section: Discussionmentioning

confidence: 96%

Enantioselective hydrogenation of ethyl pyruvate over cinchonidine-Pt/Al2O3 catalyst. A reaction kinetic approach

2006

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A new reaction kinetic approach was used to describe the enantioselective hydrogenation of ethyl pyruvate over cinchona-Pt catalyst. The above reaction was considered as the sum of two parallel reactions: (i) racemic hydrogenation resulting in R-and S-product in equal amount and (ii) enantioselective hydrogenation leading to the exclusive formation of one of the two optically isomers. New terms such as acc diff and k e /k r (where k e and k r are the rate constants of the enantioselective and racemic hydrogenation, respectively) were introduced to characterize the relationship between the enantioselective and the racemic hydrogenation reactions. Results obtained show that the formation of R-product is rate accelerated, while the formation of S-product is decelerated. The results indicate also that the overall rate increase is a kinetic phenomenon and cannot be attributed to the suppression of the poisoning effect of CO or oligomers formed from ethyl pyruvate. The strong rate acceleration effect of achiral tertiary amines (ATAs) added to the reaction mixture was attributed to the decrease of the loss of modifier during the hydrogenation experiments.

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“…It is believed that an important factor in achieving high enantioselectivity is that the interaction between modifier and reactant induces a rate enhancement [24] such that the contribution to the product distribution from the racemic reaction at unmodified sites is relatively insignificant.…”

Section: Rate Enhancement At Modified Sites (K Mod ) K Rac )mentioning

confidence: 99%

Fundamental Investigations of Enantioselective Heterogeneous Catalysis

et al. 2011

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Enantioselective catalysis is an increasingly important method of providing enantiomeric compounds for the pharmaceutical and agrochemical industries. To date, heterogeneous catalysts have failed to match the industrial impact achieved by homogeneous systems. One successful approach to the creation of heterogeneous enantioselective catalysts has involved the modification of conventional metal particle catalysts by the adsorption of chiral molecules. This article examines the contribution of effects such as chiral recognition and amplification to these types of system and how insight provided by surface science model studies may be exploited in the design of more effective catalysts.

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Origin of enhanced rate in the platinum-catalysed enantioselective hydrogenation of methyl pyruvate

Cited by 67 publications

References 4 publications

Anomalous behavior of rigid cinchona alkaloids in the enantioselective hydrogenation of ethyl pyruvate in an aprotic solvent

Anomalous behavior of rigid cinchona alkaloids in the enantioselective hydrogenation of ethyl pyruvate in an aprotic solvent

Enantioselective hydrogenation of ethyl pyruvate over cinchonidine-Pt/Al2O3 catalyst. A reaction kinetic approach

Fundamental Investigations of Enantioselective Heterogeneous Catalysis

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