ELECTROSTATIC STABILIZATION CAN EXPLAIN THE UNEXPECTED ACIDITY OF CARBON ACIDS IN ENZYME-CATALYZED REACTIONS
ELECTROSTATIC STABILIZATION CAN EXPLAIN THE UNEXPECTED ACIDITY OF CARBON ACIDS IN ENZYME-CATALYZED REACTIONS
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DOI：
10.1021/ja00077a063
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发表时间：
1993-12-01
影响因子：
15
通讯作者：
KLUGER, R
中科院分区：
文献类型：
--
作者：
GUTHRIE, JP;KLUGER, R
与最近的声明相反，亲电催化不足以解释观察到的作为碳酸的羧酸反应的酶催化作用(Gerlt，J.A.；Kozarich，J.W.；Kenyon，G.L.；Gassman，P.G.J.Am化学。SoC。1991年、113、9667年。Gassman，P.G.J.Am化学。SoC。1992、114、5928-5934)。这个问题本质上是热力学问题。烯基上的负电荷允许静电稳定的可能性，这在低极性的介质中可以很大；这可以提供足够的能量来允许快速反应。
Electrophilic catalysis is inadequate to explain the observed enzymic catalysis of reactions of carboxylic acids as carbon acids, contrary to 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 possibility of electrostatic stabilization, which can be large in a medium of low polarity; this could supply enough energy to allow rapid reaction.