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A Flavoprotein Dioxygenase Steers Bacterial Tropone Biosynthesis via Coenzyme A-Ester Oxygenolysis and Ring Epoxidation
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2021-07-01 , DOI: 10.1021/jacs.1c04996 Ying Duan 1 , Marina Toplak 1 , Anwei Hou 2 , Nelson L Brock 3 , Jeroen S Dickschat 2, 3 , Robin Teufel 1
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2021-07-01 , DOI: 10.1021/jacs.1c04996 Ying Duan 1 , Marina Toplak 1 , Anwei Hou 2 , Nelson L Brock 3 , Jeroen S Dickschat 2, 3 , Robin Teufel 1
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Bacterial tropone natural products such as tropolone, tropodithietic acid, or the roseobacticides play crucial roles in various terrestrial and marine symbiotic interactions as virulence factors, antibiotics, algaecides, or quorum sensing signals. We now show that their poorly understood biosynthesis depends on a shunt product from aerobic CoA-dependent phenylacetic acid catabolism that is salvaged by the dedicated acyl-CoA dehydrogenase-like flavoenzyme TdaE. Further characterization of TdaE revealed an unanticipated complex catalysis, comprising substrate dehydrogenation, noncanonical CoA-ester oxygenolysis, and final ring epoxidation. The enzyme thereby functions as an archetypal flavoprotein dioxygenase that incorporates both oxygen atoms from O2 into the substrate, most likely involving flavin-N5-peroxide and flavin-N5-oxide species for consecutive CoA-ester cleavage and epoxidation, respectively. The subsequent spontaneous decarboxylation of the reactive enzyme product yields tropolone, which serves as a key virulence factor in rice panicle blight caused by pathogenic edaphic Burkholderia plantarii. Alternatively, the TdaE product is most likely converted to more complex sulfur-containing secondary metabolites such as tropodithietic acid from predominant marine Rhodobacteraceae (e.g., Phaeobacter inhibens).
中文翻译：
黄素蛋白双加氧酶通过辅酶 A-酯氧解和环环氧化控制细菌肌钙蛋白的生物合成
细菌托酚酮天然产物，如托酚酮、托托二硫代酸或玫瑰杀菌剂，在各种陆地和海洋共生相互作用中起着至关重要的作用，如毒力因子、抗生素、除藻剂或群体感应信号。我们现在表明，它们知之甚少的生物合成依赖于需氧 CoA 依赖性苯乙酸分解代谢的分流产物，该分流产物由专用的酰基辅酶 A 脱氢酶样黄素酶 TdaE 挽救。TdaE 的进一步表征揭示了一种意想不到的复杂催化，包括底物脱氢、非经典 CoA-酯氧解和最终环氧化。因此，该酶作为一种典型的黄素蛋白双加氧酶发挥作用，它结合了来自 O 2的两个氧原子进入底物，最有可能涉及黄素-N5-过氧化物和黄素-N5-氧化物物质，分别用于连续的 CoA-酯裂解和环氧化。随后反应性酶产物的自发脱羧产生托酚酮，它是由病原性土壤植物伯克霍尔德菌引起的水稻穗枯病的关键毒力因子。或者， TdaE产物最有可能转化为更复杂的含硫次生代谢物，例如来自主要海洋红杆菌科（如抑制嗜热菌）的原二硫代硫酸。
更新日期：2021-07-14
中文翻译：
黄素蛋白双加氧酶通过辅酶 A-酯氧解和环环氧化控制细菌肌钙蛋白的生物合成
细菌托酚酮天然产物，如托酚酮、托托二硫代酸或玫瑰杀菌剂，在各种陆地和海洋共生相互作用中起着至关重要的作用，如毒力因子、抗生素、除藻剂或群体感应信号。我们现在表明，它们知之甚少的生物合成依赖于需氧 CoA 依赖性苯乙酸分解代谢的分流产物，该分流产物由专用的酰基辅酶 A 脱氢酶样黄素酶 TdaE 挽救。TdaE 的进一步表征揭示了一种意想不到的复杂催化，包括底物脱氢、非经典 CoA-酯氧解和最终环氧化。因此，该酶作为一种典型的黄素蛋白双加氧酶发挥作用，它结合了来自 O 2的两个氧原子进入底物，最有可能涉及黄素-N5-过氧化物和黄素-N5-氧化物物质，分别用于连续的 CoA-酯裂解和环氧化。随后反应性酶产物的自发脱羧产生托酚酮，它是由病原性土壤植物伯克霍尔德菌引起的水稻穗枯病的关键毒力因子。或者， TdaE产物最有可能转化为更复杂的含硫次生代谢物，例如来自主要海洋红杆菌科（如抑制嗜热菌）的原二硫代硫酸。
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