Catalysis of a Flavoenzyme-Mediated Amide Hydrolysis

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• 作者：Tathagata Mukherjee ; Yang Zhang ; Sameh Abdelwahed ; Steven E. Ealick ; Tadhg P. Begley
• 刊名：Journal of the American Chemical Society
• 出版年：2010
• 出版时间：April 28, 2010
• 年：2010
• 卷：132
• 期：16
• 页码：5550-5551
• 全文大小：209K
• 年卷期：v.132,no.16(April 28, 2010)
• ISSN：1520-5126

文摘

A new pyrimidine catabolic pathway (the Rut pathway) was recently discovered in Escherichia coli K12. In this pathway, uracil is converted to 3-hydroxypropionate, ammonia, and carbon dioxide. The seven-gene Rut operon is required for this conversion. Here we demonstrate that the flavoenzyme RutA catalyzes the initial uracil ring-opening reaction to give 3-ureidoacrylate. This reaction, while formally a hydrolysis reaction, proceeds by an oxidative mechanism initiated by the addition of a flavin hydroperoxide to the C4 carbonyl. While peroxide-catalyzed amide hydrolysis has chemical precedent, we are not aware of a prior example of analogous chemistry catalyzed by flavin hydroperoxides. This study further illustrates the extraordinary catalytic versatility of the flavin cofactor.