TY - JOUR
T1 - Mechanism of hydrolysis of phosphorylethanolamine diesters. Intramolecular nucleophilic amine participation
AU - Lazarus, Robert A.
AU - Benkovic, Patricia A.
AU - Benkovic, Stephan J.
PY - 1980
Y1 - 1980
N2 - Intramolecular displacement reactions at phosphorus have been examined in a series of N-alkyl-O-arylphosphoryl-ethanolamines in water at 35°C. The examination of the pH-rate profiles and the direct observation by 31P n.m.r. of the reaction products implicate a nucleophilic role for the amine. A rate enhancement of 106-107 is observed. Structure-reactivity correlations derived by changing the pKa of the amine and leaving group yield values for βnuc ≃0.7 and β1g ≃-1.25 and support an uncoupled concerted mechanism. A discussion of the mechanisms of nucleophilic reactions involving amines and oxyanions with inter- and intra-molecular phosphate di- and tri-esters is presented.
AB - Intramolecular displacement reactions at phosphorus have been examined in a series of N-alkyl-O-arylphosphoryl-ethanolamines in water at 35°C. The examination of the pH-rate profiles and the direct observation by 31P n.m.r. of the reaction products implicate a nucleophilic role for the amine. A rate enhancement of 106-107 is observed. Structure-reactivity correlations derived by changing the pKa of the amine and leaving group yield values for βnuc ≃0.7 and β1g ≃-1.25 and support an uncoupled concerted mechanism. A discussion of the mechanisms of nucleophilic reactions involving amines and oxyanions with inter- and intra-molecular phosphate di- and tri-esters is presented.
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U2 - 10.1039/P29800000373
DO - 10.1039/P29800000373
M3 - Article
AN - SCOPUS:37049101858
SN - 1472-779X
SP - 373
EP - 379
JO - Journal of the Chemical Society, Perkin Transactions 2
JF - Journal of the Chemical Society, Perkin Transactions 2
IS - 2
ER -