OMP 脱羧酶：磷酰二阴离子结合能被用来稳定乙烯基碳负离子中间体。
OMP decarboxylase: phosphodianion binding energy is used to stabilize a vinyl carbanion intermediate.
机构信息
Department of Chemistry, University at Buffalo, Buffalo, New York 14260, USA.
出版信息
J Am Chem Soc. 2011 May 4;133(17):6545-8. doi: 10.1021/ja201734z. Epub 2011 Apr 12.
Abstract
Orotidine 5'-monophosphate decarboxylase (OMPDC) catalyzes the exchange for deuterium from solvent D(2)O of the C-6 proton of 1-(β-d-erythrofuranosyl)-5-fluorouracil (FEU), a phosphodianion truncated product analog. The deuterium exchange reaction of FEU is accelerated 1.8 × 10(4)-fold by 1 M phosphite dianion (HPO(3)(2-)). This corresponds to a 5.8 kcal/mol stabilization of the vinyl carbanion-like transition state, which is similar to the 7.8 kcal/mol stabilization of the transition state for OMPDC-catalyzed decarboxylation of a truncated substrate analog by bound HPO(3)(2-). These results show that the intrinsic binding energy of phosphite dianion is used in the stabilization of the vinyl carbanion-like transition state common to the decarboxylation and deuterium exchange reactions.
摘要
乳清酸 5'-单磷酸脱羧酶（OMPDC）催化 1-（β-d-呋喃核糖基）-5-氟尿嘧啶（FEU）的 C-6 质子与溶剂 D（2）O 中氘的交换反应，FEU 是磷酸二阴离子截断产物类似物。在 1 M 亚磷酸盐二阴离子（HPO（3）（2-））的作用下，FEU 的氘交换反应加速了 1.8×10（4）倍。这相当于乙烯碳负离子类似过渡态的 5.8 kcal/mol 稳定化，与 OMPDC 催化的截断底物类似物的脱羧反应中结合的 HPO（3）（2-）稳定化的 7.8 kcal/mol 稳定化相似。这些结果表明，亚磷酸盐二阴离子的固有结合能用于稳定脱羧和氘交换反应共有的乙烯碳负离子类似过渡态。
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