Evidence for a 1,3-Dipolar Cyclo-addition Mechanism in the Decarboxylation of Phenylacrylic Acids Catalyzed by Ferulic Acid Decarboxylase,Journal of the American Chemical Society

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Evidence for a 1,3-Dipolar Cyclo-addition Mechanism in the Decarboxylation of Phenylacrylic Acids Catalyzed by Ferulic Acid Decarboxylase
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2017-08-02 00:00:00 , DOI: 10.1021/jacs.7b05060
Kyle L. Ferguson ₁ , Joseph D. Eschweiler ₁ , Brandon T. Ruotolo ₁ , E. Neil G. Marsh _{1,

2}

Affiliation

Ferulic acid decarboxylase catalyzes the decarboxylation of phenylacrylic acid using a newly identified cofactor, prenylated flavin mononucleotide (prFMN). The proposed mechanism involves the formation of a putative pentacyclic intermediate formed by a 1,3 dipolar cyclo-addition of prFMN with the α–β double bond of the substrate, which serves to activate the substrate toward decarboxylation. However, enzyme-catalyzed 1,3 dipolar cyclo-additions are unprecedented and other mechanisms are plausible. Here we describe the use of a mechanism-based inhibitor, 2-fluoro-2-nitrovinylbenzene, to trap the putative cyclo-addition intermediate, thereby demonstrating that prFMN can function as a dipole in a 1,3 dipolar cyclo-addition reaction as the initial step in a novel type of enzymatic reaction.

中文翻译：

阿魏酸脱羧酶催化苯基丙烯酸脱羧中1,3-偶极环加成机理的证据

阿魏酸脱羧酶使用新鉴定的辅因子，异戊烯基黄素单核苷酸（prFMN）催化苯基丙烯酸的脱羧。拟议中的机制涉及通过推定prFMN与底物的α-β双键的1,3双极环加成形成假定的五环中间体，该五环中间体用于激活底物进行脱羧反应。然而，酶催化的1，3偶极环加成是空前的，其他机制似乎是合理的。在这里，我们描述了使用基于机理的抑制剂2-氟-2-硝基乙烯基苯来俘获推定的环加成中间体，从而证明prFMN可以在1,3偶极环加成反应中作为偶极起作用。新型酶促反应的第一步。

更新日期：2017-08-03

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