(4R,5S,6S,8R,9R,12R,13R)-4,8,12-triethyl-5-hydroxy-6-methyl-8,9;12,13-diepoxytetradecan-3-one | 1227153-86-7

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: (4R,5S,6S,8R,9R,12R,13R)-4,8,12-triethyl-5-hydroxy-6-methyl-8,9;12,13-diepoxytetradecan-3-one
• 英文别名: (4R,5S,6S)-4-ethyl-7-[(2R,3R)-2-ethyl-3-[2-[(2R,3R)-2-ethyl-3-methyloxiran-2-yl]ethyl]oxiran-2-yl]-5-hydroxy-6-methylheptan-3-one
• CAS: 1227153-86-7
• 化学式: C₂₁H₃₈O₄
• 分子量: 354.53
• InChiKey: JGFVWNIOHJKPSD-LZBRDQHESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  25
• 可旋转键数：
  12
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.95
• 拓扑面积：
  62.4
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (4R,5S,6S,8R,9R,12R,13R)-4,8,12-triethyl-5-hydroxy-6-methyl-8,9;12,13-diepoxytetradecan-3-one 在 Lsd₁₉ 作用下， 以13%的产率得到Lasalocid ketone
  参考文献：
  名称：

  Sequential Enzymatic Epoxidation Involved in Polyether Lasalocid Biosynthesis

  摘要：

  Enantioselective epoxidation followed by regioselective epoxide opening reaction are the key processes in construction of the polyether skeleton. Recent genetic analysis of ionophore polyether biosynthetic gene dusters suggested that flavin-containing monooxygenases (FMOs) could be involved in the oxidation steps. In vivo and in vitro analyses of Lsd18, an FMO involved in the biosynthesis of polyether lasalocid, using simple olefin or truncated diene of a putative substrate as substrate mimics demonstrated that enantioselective epoxidation affords natural type mono- or bis-epoxide in a stepwise manner. These findings allow us to figure out enzymatic polyether construction in lasalocid biosynthesis.

  DOI：

  10.1021/ja301386g
• 作为产物：
  描述：

  在 NADPH 、 FAD 、 β-烟酰胺腺嘌呤二核苷酸 作用下， 生成 (4R,5S,6S,8R,9R,12R,13R)-4,8,12-triethyl-5-hydroxy-6-methyl-8,9;12,13-diepoxytetradecan-3-one
  参考文献：
  名称：

  Sequential Enzymatic Epoxidation Involved in Polyether Lasalocid Biosynthesis

  摘要：

  Enantioselective epoxidation followed by regioselective epoxide opening reaction are the key processes in construction of the polyether skeleton. Recent genetic analysis of ionophore polyether biosynthetic gene dusters suggested that flavin-containing monooxygenases (FMOs) could be involved in the oxidation steps. In vivo and in vitro analyses of Lsd18, an FMO involved in the biosynthesis of polyether lasalocid, using simple olefin or truncated diene of a putative substrate as substrate mimics demonstrated that enantioselective epoxidation affords natural type mono- or bis-epoxide in a stepwise manner. These findings allow us to figure out enzymatic polyether construction in lasalocid biosynthesis.

  DOI：

  10.1021/ja301386g

文献信息

• Enzymatic Epoxide-Opening Cascades Catalyzed by a Pair of Epoxide Hydrolases in the Ionophore Polyether Biosynthesis
  作者：Atsushi Minami、Akira Migita、Daiki Inada、Kinya Hotta、Kenji Watanabe、Hiroki Oguri、Hideaki Oikawa

  DOI：10.1021/ol200100e

  日期：2011.4.1

  Our recent findings of the first epoxide hydrolase Lsd19, involved in lasalocid A biosynthesis, led us to investigate a long-standing controversial issue on the mechanism of enzymatic epoxide-opening cascades. The site-directed mutagenesis and domain dissection analysis to reveal the mechanism of the reaction catalyzed by Lsd19 is examined, especially in the role of acidic amino acid pair and catalytic

  我们最近发现的第一个环氧水解酶Lsd19参与了lasalocid A的生物合成，这使我们研究了酶促环氧开放级联反应机制中一个长期存在的争议性问题。进行了定点诱变和结构域解剖分析，揭示了Lsd19催化反应的机理，特别是在酸性氨基酸对和催化结构域中的作用。
• Intriguing Substrate Tolerance of Epoxide Hydrolase Lsd19 Involved in Biosynthesis of the Ionophore Antibiotic Lasalocid A
  作者：Yusuke Matsuura、Yoshihiro Shichijo、Atsushi Minami、Akira Migita、Hiroki Oguri、Mami Watanabe、Tetsuo Tokiwano、Kenji Watanabe、Hideaki Oikawa

  DOI：10.1021/ol100541e

  日期：2010.5.21

  Recently, we reported that the epoxide hydrolase Lsd19, the first enzyme shown to catalyze epoxide-opening cascades, can catalyze the conversion of a putative bisepoxide intermediate to polyether antibiotic lasalocid, which involves energetically disfavored 6-endo-tet cyclization of the epoxy alcohol. Here, we examined the substrate tolerance of Lsd19. Lsd19 accepts various substrate analogues differing in the left segment of lasalocid and epoxide stereochemistry to afford either THF-THP or THF-THF products with excellent regioselectivity.
• Sequential Enzymatic Epoxidation Involved in Polyether Lasalocid Biosynthesis
  作者：Atsushi Minami、Mayu Shimaya、Gaku Suzuki、Akira Migita、Sandip S. Shinde、Kyohei Sato、Kenji Watanabe、Tomohiro Tamura、Hiroki Oguri、Hideaki Oikawa

  DOI：10.1021/ja301386g

  日期：2012.5.2

  Enantioselective epoxidation followed by regioselective epoxide opening reaction are the key processes in construction of the polyether skeleton. Recent genetic analysis of ionophore polyether biosynthetic gene dusters suggested that flavin-containing monooxygenases (FMOs) could be involved in the oxidation steps. In vivo and in vitro analyses of Lsd18, an FMO involved in the biosynthesis of polyether lasalocid, using simple olefin or truncated diene of a putative substrate as substrate mimics demonstrated that enantioselective epoxidation affords natural type mono- or bis-epoxide in a stepwise manner. These findings allow us to figure out enzymatic polyether construction in lasalocid biosynthesis.