Stereochemistry of enzymatic reactions

Guy Lemiere was born in Antwerp, Belgium, and studied chemistry at the Universities of Antwerp and Ghent. In 1975 he obtained a PhD in organic chemistry from the University of Antwerp on the subject Study on enzymatic in vivo and in vitro reductions of cyclic ketones . He built up all his academic career at the University of Antwerp. His scientific interests evolved from the stereochemistry of enzymatic reactions to natural products and further to heterocyclic chemistry, especially the chemistry of pyridazines. In 2004 he organized together with Bert Maes the 9th International Symposium on the Chemistry and Pharmacology of Pyridazines in Antwerp. He is an author of around 80 scientific papers. 

R. S. Phillips, Temperature effeds on stereochemistry of enzymatic reactions, Enzyme Microb. Technol. 1992, 14, 417-419. 

Nucleosides, regioselective elongation of carbon chain of 86YGK9. Nucleosides, silyl method of their synthesis (monograph) 85MI17. Nucleosides, stereochemistry of enzymatic reactions of phosphates in ... 

The cis effect can also determine the stereochemistry of enzymatic reactions. The most prominent example is the metabolism of toxic fluoroacetate in the Krebs... 

The aim of biosynthetic experiments with fungal metabolites is to establish the structure of the building blocks, the order in which they are assembled, the way in which chains are folded to form the carbon skeleton and the sequence interrelating precursors with the final metabolite. Biosynthesis is concerned with both sequences and reaction mechanisms. The sequence of the biosynthetic events, the role of intermediates and the stereochemistry of enzymatic reactions can be studied with appropriately isotopically-labelled substrates and with structural analogues of the natural intermediates. The chemical enzymology of individual steps and the role of key components and structures of the enzyme may be studied with isolated enzyme systems obtained from fungi. The features that determine the function of the enzyme and which control its activity may be determined by genetic studies in which mutants play an important role. 

Minimal motion rule The observed stereochemistry of enzymatic reactions usually assumes that the proposed intermediates remain oriented through consecutive steps in a minimal motion relationship to the interacting groups. The selection for minimal motion can be explained ... 

Levy, H. R., Talalay, P., Vennesland, B. The steric course of enzymatic reactions at meso carbon atoms application of hydrogen isotopes. In progress in stereochemistry (ed. de la Mare and Klyne), Vol. 3, p. 299—349. (London Butterworths 1962. 

John W. Cornforth and Vladimir Prelog Chemistry Stereochemistry of organic molecules and of enzymatic reactions... 

Differences between the stereochemistries of enzymatic and nonenzymatic reactions... 

Maturation of the petro-chemical industry, environmental pressures for "clean chemistry" and the explosive development of biotechnology have increased interest in the application of enzymatic processes to organic synthesis. Enzymatic processes play an increasing role in the generation of chiral pharmaceutical intermediates, water-soluble materials and biopolymers. One problem in the development of enzymatic reactions for organic synthesis is the prediction of the stereochemistry of reaction. Reliable models for prediction of stereochemistry are needed to broaden the application of enzymes to organic synthesis. 

Koshland, D.E. (1953) Stereochemistry and the mechanism of enzymatic reactions. Biol. Rev. Camb. Philos. Soc.,... 

A second aspect of the stereochemistry of NADH reactions results from NADH having two hydrogens at C4, either of which could, in principle, be transferred as a hydride in a reduction process. For a given enzymatic reaction, however, only one specific hydride from C4 in NADH is transferred. Just which hydride is transferred depends on the specific enzyme involved, and we designate it by a useful extension of stereochemical nomenclature. The hydrogens at C4 of NADH are said to be prochiral. We designate one pro-R, and the other pro-S,... 

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