OMP Decarboxylase: Phosphodianion Binding Energy Is Used To Stabilize a Vinyl Carbanion Intermediate,Journal of the American Chemical Society

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OMP Decarboxylase: Phosphodianion Binding Energy Is Used To Stabilize a Vinyl Carbanion Intermediate
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2011-05-04 , DOI: 10.1021/ja201734z
Bogdana Goryanova ₁ , Tina L Amyes , John A Gerlt , John P Richard

Affiliation

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.

中文翻译：

OMP 脱羧酶：磷酸二氢阴离子结合能用于稳定乙烯基碳负离子中间体

奥罗替丁 5'-单磷酸脱羧酶 (OMPDC) 催化 1-(β-d-赤呋喃糖基)-5-氟尿嘧啶 (FEU) 的 C-6 质子的溶剂 D(2)O 中的氘交换，这是一种磷酸二阴离子截短的产物类似物. FEU 的氘交换反应被 1 M 亚磷酸酯二价阴离子 (HPO(3)(2-)) 加速了 1.8 × 10(4) 倍。这对应于类乙烯基碳负离子过渡态的 5.8 kcal/mol 稳定性，这类似于 OMPDC 催化的结合 HPO(3)(2 -)。这些结果表明，亚磷酸酯二阴离子的固有结合能用于稳定脱羧和氘交换反应中常见的乙烯基碳负离子状过渡态。

更新日期：2011-05-04

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