(E)-oxacycloheneicos-11-en-2-one

• 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)-oxacycloheneicos-11-en-2-one
• 英文别名: oxacyclohenicos-11-en-2-one；(11E)-1-oxacyclohenicos-11-en-2-one
• 化学式: C₂₀H₃₆O₂
• 分子量: 308.505
• InChiKey: LOPQEODTCZEUEM-OWOJBTEDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.7
• 重原子数：
  22
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.85
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (E)-oxacycloheneicos-11-en-2-one 、 乙烯 、 六氯化钨 生成 undec-10-enoic acid undec-10-enyl ester
  参考文献：
  名称：

  TSUJI JIRO; HASHIGUCHI SHOHEI, TETRAHEDRON LETT., 1980, 21, NO 31, 2955-2958

  摘要：

  DOI：
• 作为产物：
  描述：

  10-十一烯-1-醇 在 ruthenium carbene complex 硫酸 作用下， 以 苯 为溶剂， 反应 29.0h， 生成 (E)-oxacycloheneicos-11-en-2-one
  参考文献：
  名称：

  Litinas, Konstantinos E.; Salteris, Basil E., Journal of the Chemical Society. Perkin transactions I, 1997, # 19, p. 2869 - 2872

  摘要：

  DOI：

文献信息

• Tishchenko reactions of aldehydes promoted by diisobutylaluminum hydride and its application to the macrocyclic lactone formation
  作者：Yung-Son Hon、Ying-Chieh Wong、Chun-Ping Chang、Cheng-Han Hsieh

  DOI：10.1016/j.tet.2007.08.074

  日期：2007.11

  Aliphatic aldehydes react with catalytic amount of Dibal-H in n-pentane to give the corresponding Tishchenko products in good to excellent yields. On contrary, α-silyloxy aldehydes give α-silyloxy ketones via Oppenauer oxidation under similar condition. Tishchenko reaction of ω-alkene aldehydes followed by RCM and hydrogenation affords a convenient method to prepare the 11–37 membered macrocyclic lactones

  脂肪醛与正戊烷中催化量的Dibal-H反应，以良好至极好的收率得到相应的季申科产品。相反，在类似条件下，α-甲硅烷氧基醛通过Oppenauer氧化生成α-甲硅烷氧基酮。ω-烯烃醛的Tishchenko反应，然后进行RCM和氢化提供了一种方便的方法来制备11-37元大环内酯。
• Kinetically E-selective macrocyclic ring-closing metathesis
  作者：Xiao Shen、Thach T. Nguyen、Ming Joo Koh、Dongmin Xu、Alexander W. H. Speed、Richard R. Schrock、Amir H. Hoveyda

  DOI：10.1038/nature20800

  日期：2017.1

  stereoselectively to E-macrocyclic alkenes. The reaction is promoted by a molybdenum monoaryloxide pyrrolide complex and affords products at a yield of up to 73 per cent and an E/Z ratio greater than 98/2. We highlight the utility of the approach by preparing recifeiolide (a 12-membered-ring antibiotic) and pacritinib (an 18-membered-ring enzyme inhibitor), the Z-isomer of which is less potent than the

  大环化合物是新药开发的核心，但制备它们可能具有挑战性，因为必须克服能量障碍才能将非环状前体的两端融合在一起，例如烯烃（也称为烯烃） ）。为此，被称为闭环复分解 (RCM) 的催化过程允许获得无数具有生物活性的大环有机分子，甚至可以用于大规模生产。在这种情况下，立体选择性通常很关键：大环化合物的效力取决于其烯烃的立体化学；或者，可以对化合物的一种异构体进行立体选择性修饰（例如二羟基化）。已经报道了动力学控制的 Z 选择性 RCM 反应，但唯一可用的用于获取大环 E-烯烃的复分解方法需要通过乙烯解选择性去除立体异构混合物的 Z 组分，如果 E/Z 比接近统一，则会牺牲大量材料。使用乙烯还会导致不定的烯烃异构化——当 E-烯烃在能量上不太受欢迎时，这是一个特别严重的问题。在这里，我们表明含有 E-烯基-B（频哪醇）基团的二烯，广泛用于催化交叉偶联，具有必要的电子和空间属性，使它们能够立体选择性地转化为
• A new method for the polymer-supported synthesis of cyclic oligoesters for potential applications in macrocyclic lactone synthesis and combinatorial chemistry
  作者：Clare L. Ruddick、Philip Hodge、Anthony Cook、Andrew J. McRiner

  DOI：10.1039/b110528k

  日期：2002.2.22

  for the small-scale combinatorial synthesis of copolyesters. For both of these applications the fact that the PS syntheses afford families of COs is not a problem because the applications involve the establishment of equilibria into which all of the COs can feed. Finally, these PS reactions may provide a useful approach to the small-scale synthesis of macrocyclic lactones with 15 or more ring atoms

  将ω-羟基链烷羧酸连接到Merrifield磁珠上，然后用催化量的 二正丁基氧化锡 在 氯苯在133°C下进行4–18小时，形成了相应的环状低聚物（COs）作为主要的可溶性产物（> 92％），产率为56–83％。用类似的方法获得了类似的结果。聚合物-支持的 （聚苯乙烯） 蓖麻油酸具有仲羟基，但尝试与PS进行类似反应 石胆酸失败的。聚苯乙烯20-羟基二十碳十烯酸 和 N-（11-羟基十一烷酰基）-11-氨基十一烷酸反应良好，可生成CO，其中环状单体是主要产物。分离出这些环状单体的样品。后两个羟基酸也成功地组装在磁珠上（前一个使用烯烃复分解），然后进行环寡聚。该PS合成方法有多种可能的应用。因此，CO可以通过酯交换反应用于制备可溶性的大环或用作小规模共聚聚酯合成的原料。对于这两种应用，PS合成提供了CO族这一事实不是问题，因为应用涉及建立所有CO都可以供入的平衡。最终，这些PS反应可能为小规模合成苯胺提供有用的方法。大环内酯
• Catalyst complex with a heterocyclic carbene ligand
  申请人：University Of New Orleans Foundation

  公开号：EP2116302A1

  公开（公告）日：2009-11-11

  Catalytic complexes including a metal atom selected from ruthenium or osmium having at least one anionic ligand, at least one nucleophilic carbene ligand, a further ligand and an alkylidene, vinylidene, or allenylidene ligand. The complexes are highly stable to air, moisture and thermal degradation. The complexes are designed to efficiently carry out a variety of ring-closing olefin metathesis reactions.

  催化络合物包括一个金属原子，该金属原子选自钌或锇，具有至少一种阴离子配体、至少一种亲核碳烯配体、另一种配体以及亚烷基、亚乙烯基或亚烯基配体。这些配合物对空气、湿气和热降解非常稳定。这些配合物可有效地进行各种闭环烯烃偏析反应。
• Highly Selective Macrocycle Formations by Metathesis Catalysts Fixated in Nanopores
  作者：Joo-Eun Jee、Jian Liang Cheong、Jaehong Lim、Cheng Chen、Soon Hyeok Hong、Su Seong Lee

  DOI：10.1021/jo302823w

  日期：2013.4.5

  Ruthenium-based metathesis catalysts immobilized on mesocellular siliceous foam (MCF) bearing large nanopores proved highly efficient and selective for macrocyclic ring-closing metathesis (RCM). Kinetic studies revealed that the homogeneous counterpart exhibited far higher activity that accounted for more oligomerization pathways and resulted in less macrocyclization products. Meanwhile, the immobilized catalysts showed lower conversion rates leading to higher yields of macrocyclic products in a given reaction time, with conversion rates and yields dependent upon pore size, catalyst loading density, and linker length. The macrocycle formations via RCM were accelerated by increasing the pore size and decreasing the catalyst loading density while retaining the comparably high yield. The catalysts immobilized on MCF, of which silica surface is rigid and pores are relatively large, showed high conversion rates and yields compared with an analogue immobilized on TentaGel resins, of which backbone becomes flexible upon swelling in the reaction medium. It is noteworthy that the selectivity for the macrocyclic RCM can be significantly improved by tuning the catalyst initiation rates via immobilization onto the support materials in which well-defined three-dimentional network of large nanopores are deployed.