Stereoelectronic Control in the Phosphorylation of Serine Esterases.
Final rept. 1 Sep 85-31 Aug 86,
PURDUE UNIV LAFAYETTE IN
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Several approaches to the study of stereo-electronic control in the enzymatic reactions of organophosphorus compounds are discussed. This stereoelectronic control involves weakening of a P-O ester bond by antiperiplanar interactions with oxygen or nitrogen lone pairs. The first stereoelectronic control involves weakening of a P-O ester bond by antiperiplanar interactions with oxygen or nitrogen lone pairs. The 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. Phosphorus 31 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.
- Organic Chemistry