Stereoelectronic Control in the Phosphorlyation of Serine Esterases.
Final rept. 1 Aug 83-31 Jul 85,
PURDUE UNIV LAFAYETTE IN
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Our research has involved several approaches to the study of stereo-electronic control in the enzymatic reactions of organophosphorus compounds. This stereoelectronic control involves weakening of a P-O ester bond by antiperi-planar interactions with oxygen or nitrogen lone pairs. Our first approach has been to study the kinetics and mechanism of enzymatic reaction of a number of conformationally restricted phosphorus compounds to determine the importance of stereoelectronic effects in enzymatic phosphorylation at phosphorus. The stereochemistry of reaction of phosphate esters has extended to the non-enzymatic and enzymatic reactions of phosphate triesters. P31 NMR has been used to monitor the stereochemistry of the enzymatic covalent modification as well as the reactivation and aging reactions of covalently phosphorylated enzymes. Ab initio molecular orbital calculations have also revealed important stereoelectronic effects. Keywords Organophosphorus, Nucleophilicity, Hydrolysis.
- Organic Chemistry