Jp. Guthrie et R. Kluger, ELECTROSTATIC STABILIZATION CAN EXPLAIN THE UNEXPECTED ACIDITY OF CARBON ACIDS IN ENZYME-CATALYZED REACTIONS, Journal of the American Chemical Society, 115(24), 1993, pp. 11569-11572
Electrophilic catalysis is inadequate to explain the observed enzymic
catalysis of reactions of carboxylic acids as carbon acids, contrary t
o recent claims (Gerlt, J. A.; Kozarich, J. W.; Kenyon, G. L.; Gassman
, P. G. J. Am. Chem. Soc. 1991, 113, 9667. Gerlt, J. A.; Gassman, P. G
. J. Am. Chem. Soc. 1992, 114, 5928-5934.). The problem is essentially
thermodynamic. The negative charge on the enolate allows the possibil
ity of electrostatic stabilization, which can be large in a medium of
low polarity; this could supply enough energy to allow rapid reaction.