Thiolysis and alcoholysis of phosphate tri- and monoesters with alkyl and aryl leaving groups. An ab initio study in the gas phase.
Phosphate esters are important compounds in living systems. Their biological reactions with alcohol and thiol nucleophiles are catalyzed by a large superfamily of phosphatase enzymes. However, very little is known about the intrinsic reactivity of these nucleophiles with phosphorus centers. We have performed ab initio calculations on the thiolysis and alcoholysis at phosphorus of trimethyl phosphate, dimethyl phenyl phosphate, methyl phosphate, and phenyl phosphate. Results in the gas phase are a reference for the study of the intrinsic reactivity of these compounds. Thiolysis of triesters was much slower and less favorable than the corresponding alcoholysis. Triesters reacted through an associative mechanism. Monoesters can react by both associative and dissociative mechanisms. The basicity of the attacking and leaving groups and the possibility of proton transfers can modulate the reaction mechanisms. Intermediates formed along associative reactions did not follow empirically proposed rules for ligand positioning. Our calculations also allow re-interpretation of some experimental results, and new experiments are proposed to trace reactions that are normally not observed, both in the gas phase and in solution.
Arantes
Guilherme Menegon
GM
Instituto de Química, Universidade de São Paulo, Av. Lineu Prestes 748, 05508-900, São Paulo, SP, Brasil. gma@dinamicas.art.br
Chaimovich
Hernan
H
D000438:Alcohols / Q000737:chemistry*; D000465:Algorithms; D002244:Carbon / Q000737:chemistry; D002384:Catalysis; D005740:Gases; D008024:Ligands; D010755:Organophosphates / Q000737:chemistry*; D009943:Organophosphorus Compounds / Q000737:chemistry; D012996:Solutions / Q000737:chemistry; D013438:Sulfhydryl Compounds / Q000737:chemistry*
D000438:Alcohols; D005740:Gases; D008024:Ligands; D010755:Organophosphates; D009943:Organophosphorus Compounds; D012996:Solutions; D013438:Sulfhydryl Compounds; C074782:phenylphosphate; D002244:Carbon; C007477:dimethyl phosphate; C003715:trimethyl phosphate