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The spontaneous hydrolysis of 2‐pyridyl phosphate is a good model for the special mechanism for the hydrolysis of phosphate monoester monoanions
Author(s) -
Medeiros Michelle,
Manfredi Alex M.,
Kirby Anthony J.,
Nome Faruk
Publication year - 2013
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.3165
Subject(s) - chemistry , hydrolysis , phosphate , leaving group , pyridine , medicinal chemistry , organic chemistry , catalysis
The microscopic p K a of the pyridine N of the phosphate monoester 2‐pyridyl phosphate (MPP) is 2.76, significantly higher than that expected for the leaving group (RO) oxygen of a typical monoester ROPO 3 = . This favours the prototropic equilibrium considered to be the key step in the rapid hydrolysis of a typical monoester, and the observed rate of hydrolysis of the monoanion MPP − is shown to be close to that expected for the protomer MPP += , with neutral 2‐pyridone as the leaving group. Copyright © 2013 John Wiley & Sons, Ltd.