(E)-3-methyl-3,4,5,6,7,8,9,10-octahydro-1H-benzo[c]-1-oxacyclotetradecin-1-one | 10592-40-2

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 大环内酯类和类似物
• 英文名称: (E)-3-methyl-3,4,5,6,7,8,9,10-octahydro-1H-benzo[c]-1-oxacyclotetradecin-1-one
• 英文别名: (E)-3-methyl-3,4,5,6,7,8,9,10-octahydro-1H-benzo[c][1]oxacyclotetradecin-1-one；(12E)-4-methyl-3-oxabicyclo[12.4.0]octadeca-1(18),12,14,16-tetraen-2-one
• CAS: 10592-40-2；70719-37-8
• 化学式: C₁₈H₂₄O₂
• 分子量: 272.387
• InChiKey: GECZLUFSWOLKGD-XYOKQWHBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.9
• 重原子数：
  20
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  2-乙烯基-苯甲酸乙基酯 在 RuCl2(1,3-dimesityl-imidazolidin-2-yl)(PCy3)(=CHPh) 、 4-二甲氨基吡啶 、 lithium hydroxide monohydrate 、 1-(3-二甲基氨基丙基)-3-乙基碳二亚胺 作用下， 以 甲醇 、 二氯甲烷 、 水 、 甲苯 为溶剂， 反应 24.0h， 生成 (E)-3-methyl-3,4,5,6,7,8,9,10-octahydro-1H-benzo[c]-1-oxacyclotetradecin-1-one
  参考文献：
  名称：

  Resorcylic Acid Lactone Biosynthesis Relies on a Stereotolerant Macrocyclizing Thioesterase

  摘要：

  Zearalenone and radicicol are highly related resorcylic acid lactones with the rare property of having opposite stereochemical configurations of the secondary alcohol involved in lactone formation. The ability of the thioesterases from the zearalenone and radicicol biosynthetic pathways to macrocyclize both d and l configured synthetic substrate analogs was biochemically characterized and showed that both enzymes were highly stereotolerant, macrocyclizing both substrates with similar kinetic parameters. This observed stereotolerance is consistent with a proposed evolution of both natural products from a common ancestral resorcylic acid lactone.

  DOI：

  10.1021/ol502747t

文献信息

• Macrolactonization Reactions Driven by a Pentafluorobenzoyl Group**
  作者：Guillaume Force、Anna Perfetto、Robert J. Mayer、Ilaria Ciofini、David Lebœuf

  DOI：10.1002/anie.202105882

  日期：2021.9

  towards their synthesis, notably from seco-acids, a macrolactonization promoter system that is effective, selective, flexible, readily available, and, insofar as possible, compatible with manifold functional groups is still lacking. Herein, we describe a strategy that relies on the formation of a mixed anhydride incorporating a pentafluorophenyl group which, due to its high electronic activation enables

  大环内酯是一类特殊的天然和合成产品，在精细化学品和制药行业有着广泛的应用。尽管在合成方面取得了所有进展，特别是从seco-酸，一种有效的、选择性的、灵活的、容易获得的并且尽可能与多种官能团相容的大环内酯化促进剂系统仍然缺乏。在这里，我们描述了一种策略，该策略依赖于形成包含五氟苯基的混合酸酐，由于其高电子活化，可以方便地获得具有广泛多功能性的大环内酯、大二内酯和酯。进行动力学研究和 DFT 计算以合理化五氟苯基在大环内酯化反应中的反应性。
• Resorcylic Acid Lactone Biosynthesis Relies on a Stereotolerant Macrocyclizing Thioesterase
  作者：Graham W. Heberlig、Monica Wirz、Meng Wang、Christopher N. Boddy

  DOI：10.1021/ol502747t

  日期：2014.11.21

  Zearalenone and radicicol are highly related resorcylic acid lactones with the rare property of having opposite stereochemical configurations of the secondary alcohol involved in lactone formation. The ability of the thioesterases from the zearalenone and radicicol biosynthetic pathways to macrocyclize both d and l configured synthetic substrate analogs was biochemically characterized and showed that both enzymes were highly stereotolerant, macrocyclizing both substrates with similar kinetic parameters. This observed stereotolerance is consistent with a proposed evolution of both natural products from a common ancestral resorcylic acid lactone.