UDP-2-acetamido-6-deoxy-α-D-xylo-hexopyranose-5,6-ene | 1383682-85-6

• 分子结构分类: 有机化合物 - 核苷、核苷酸和类似物 - 嘧啶核苷酸
• 英文名称: UDP-2-acetamido-6-deoxy-α-D-xylo-hexopyranose-5,6-ene
• 英文别名: UDP-6-deoxy-D-N-acetylglucosamine-5,6-ene；UDP-6-deoxy-D-GlcNAc-5,6-ene；UDP-6-deoxy-5,6-ene-GlcNAc；[(2R,3R,4R,5S)-3-acetamido-4,5-dihydroxy-6-methylideneoxan-2-yl] [[(2R,3S,4R,5R)-5-(2,4-dioxopyrimidin-1-yl)-3,4-dihydroxyoxolan-2-yl]methoxy-hydroxyphosphoryl] hydrogen phosphate
• CAS: 1383682-85-6
• 化学式: C₁₇H₂₅N₃O₁₆P₂
• 分子量: 589.344
• InChiKey: BNDFCARCBRBJRX-HERNFBNESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -6.1
• 重原子数：
  38
• 可旋转键数：
  9
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.59
• 拓扑面积：
  280
• 氢给体数：
  8
• 氢受体数：
  16

反应信息

• 作为反应物：
  描述：

  UDP-2-acetamido-6-deoxy-α-D-xylo-hexopyranose-5,6-ene 在 recombinant RBTH_04254His₆ 作用下， 以 aq. buffer 为溶剂， 反应 1.0h， 生成 UDP-2-acetamido-2,6-dideoxy-β-L-arabino-hex-4-ulose
  参考文献：
  名称：

  Pen and Pal Are Nucleotide-Sugar Dehydratases That Convert UDP-GlcNAc to UDP-6-Deoxy-d-GlcNAc-5,6-ene and Then to UDP-4-Keto-6-deoxy-l-AltNAc for CMP-Pseudaminic Acid Synthesis in Bacillus thuringiensis*

  摘要：

  CMP-pseudaminic acid is a precursor required for the O-glycosylation of flagellin in some pathogenic Gram-negative bacteria, a process known to be critical in bacterial motility and infection. However, little is known about flagellin glycosylation in Gram-positive bacteria. Here, we identified and functionally characterized an operon, named Bti_pse, in Bacillus thuringiensis israelensis ATCC 35646, which encodes seven different enzymes that together convert UDP-GlcNAc to CMP-pseudaminic acid. In contrast, Gram-negative bacteria complete this reaction with six enzymes. The first enzyme, which we named Pen, converts UDP-D-GlcNAc to an uncommon UDP-sugar, UDP-6-deoxy-D-GlcNAc-5,6-ene. Pen contains strongly bound NADP(+) and has distinct UDP-GlcNAc 4-oxidase, 5,6-dehydratase, and 4-reductase activities. The second enzyme, which we named Pal, converts UDP-6-deoxy-D-GlcNAc-5,6-ene to UDP4-keto-6-deoxy-L-AltNAc. Pal is NAD(+)-dependent and has distinct UDP-6-deoxy-D-GlcNAc-5,6-ene 4-oxidase, 5,6-reductase, and 5-epimerase activities. We also show here using NMR spectroscopy and mass spectrometry that in B. thuringiensis, the enzymatic product of Pen and Pal, UDP-4-keto-6-deoxy-L-AltNAc, is converted to CMP-pseudaminic acid by the sequential activities of a C4(+)-transaminase (Pam), a 4-N-acetyltransferase (Pdi), a UDP-hydrolase (Phy), an enzyme (Ppa) that adds phosphoenolpyruvate to form pseudaminic acid, and finally a cytidylyltransferase that condenses CTP to generate CMP-pseudaminic acid. Knowledge of the distinct dehydratase-like enzymes Pen and Pal and their role in CMP-pseudaminic acid biosynthesis in Gram-positive bacteria provides a foundation to investigate the role of pseudaminic acid and flagellin glycosylation in Bacillus and their involvement in bacterial motility and pathogenicity.

  DOI：

  10.1074/jbc.m114.612747
• 作为产物：
  描述：

  尿苷5'-(2-乙酰氨基-2-脱氧-ALPHA-D-葡糖基焦磷酸酯) 在 Streptomyces chartreusis NRRL 3882 tunA 、 magnesium chloride 作用下， 生成 UDP-2-acetamido-6-deoxy-α-D-xylo-hexopyranose-5,6-ene
  参考文献：
  名称：

  衣霉素抗生素的生物合成通过独特的外糖体中间体进行

  摘要：

  衣霉素是典型的核苷类抗生素，靶向细菌肽聚糖生物合成和真核蛋白N-糖基化。了解它们不寻常的碳框架的生物合成可能会导致具有更高选择性的变体。在这里，我们展示了该途径中关键糖操纵酶的体外重演。发现 TunA 在关键 α,β-不饱和酮的还原中表现出不寻常的区域选择性。该反应的产物被证明是 TunF 的首选底物——一种将葡萄糖衍生物转化为半乳糖的差向异构酶。在链霉菌菌株中，另一个基因（tunB) 被删除，则表明生物合成在该外糖体产物处停止。这些研究证实了联合的 TunA/F 活性并描绘了代谢途径中事件的顺序。这是第一次在生物学中发现这些令人惊讶的外糖体中间体。他们认为，衣霉素氨基二醛糖核心的构建利用其烯醇醚基序以以前在自然界中未观察到的 C-C 键形成模式来创建 11 个碳链。

  DOI：

  10.1038/nchem.1351

文献信息

• Biosynthesis of the tunicamycin antibiotics proceeds via unique exo-glycal intermediates
  作者：Filip J. Wyszynski、Seung Seo Lee、Tomoaki Yabe、Hua Wang、Juan Pablo Gomez-Escribano、Mervyn J. Bibb、Soo Jae Lee、Gideon J. Davies、Benjamin G. Davis

  DOI：10.1038/nchem.1351

  日期：2012.7

  improved selectivity. Here, we demonstrate in vitro recapitulation of key sugar-manipulating enzymes from this pathway. TunA is found to exhibit unusual regioselectivity in the reduction of a key α,β-unsaturated ketone. The product of this reaction is shown to be the preferred substrate for TunF—an epimerase that converts the glucose derivative to a galactose. In Streptomyces strains in which another gene

  衣霉素是典型的核苷类抗生素，靶向细菌肽聚糖生物合成和真核蛋白N-糖基化。了解它们不寻常的碳框架的生物合成可能会导致具有更高选择性的变体。在这里，我们展示了该途径中关键糖操纵酶的体外重演。发现 TunA 在关键 α,β-不饱和酮的还原中表现出不寻常的区域选择性。该反应的产物被证明是 TunF 的首选底物——一种将葡萄糖衍生物转化为半乳糖的差向异构酶。在链霉菌菌株中，另一个基因（tunB) 被删除，则表明生物合成在该外糖体产物处停止。这些研究证实了联合的 TunA/F 活性并描绘了代谢途径中事件的顺序。这是第一次在生物学中发现这些令人惊讶的外糖体中间体。他们认为，衣霉素氨基二醛糖核心的构建利用其烯醇醚基序以以前在自然界中未观察到的 C-C 键形成模式来创建 11 个碳链。
• Pen and Pal Are Nucleotide-Sugar Dehydratases That Convert UDP-GlcNAc to UDP-6-Deoxy-d-GlcNAc-5,6-ene and Then to UDP-4-Keto-6-deoxy-l-AltNAc for CMP-Pseudaminic Acid Synthesis in Bacillus thuringiensis*
  作者：Zi Li、Soyoun Hwang、Jaime Ericson、Kyle Bowler、Maor Bar-Peled

  DOI：10.1074/jbc.m114.612747

  日期：2015.1

  CMP-pseudaminic acid is a precursor required for the O-glycosylation of flagellin in some pathogenic Gram-negative bacteria, a process known to be critical in bacterial motility and infection. However, little is known about flagellin glycosylation in Gram-positive bacteria. Here, we identified and functionally characterized an operon, named Bti_pse, in Bacillus thuringiensis israelensis ATCC 35646, which encodes seven different enzymes that together convert UDP-GlcNAc to CMP-pseudaminic acid. In contrast, Gram-negative bacteria complete this reaction with six enzymes. The first enzyme, which we named Pen, converts UDP-D-GlcNAc to an uncommon UDP-sugar, UDP-6-deoxy-D-GlcNAc-5,6-ene. Pen contains strongly bound NADP(+) and has distinct UDP-GlcNAc 4-oxidase, 5,6-dehydratase, and 4-reductase activities. The second enzyme, which we named Pal, converts UDP-6-deoxy-D-GlcNAc-5,6-ene to UDP4-keto-6-deoxy-L-AltNAc. Pal is NAD(+)-dependent and has distinct UDP-6-deoxy-D-GlcNAc-5,6-ene 4-oxidase, 5,6-reductase, and 5-epimerase activities. We also show here using NMR spectroscopy and mass spectrometry that in B. thuringiensis, the enzymatic product of Pen and Pal, UDP-4-keto-6-deoxy-L-AltNAc, is converted to CMP-pseudaminic acid by the sequential activities of a C4(+)-transaminase (Pam), a 4-N-acetyltransferase (Pdi), a UDP-hydrolase (Phy), an enzyme (Ppa) that adds phosphoenolpyruvate to form pseudaminic acid, and finally a cytidylyltransferase that condenses CTP to generate CMP-pseudaminic acid. Knowledge of the distinct dehydratase-like enzymes Pen and Pal and their role in CMP-pseudaminic acid biosynthesis in Gram-positive bacteria provides a foundation to investigate the role of pseudaminic acid and flagellin glycosylation in Bacillus and their involvement in bacterial motility and pathogenicity.