(Z)-oxacycloicos-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: (Z)-oxacycloicos-11-en-2-one
• 英文别名: Z-oxacycloicos-11-en-2-one；(11Z)-1-oxacycloicos-11-en-2-one
• 化学式: C₁₉H₃₄O₂
• 分子量: 294.478
• InChiKey: RFMKRLBLNNNHIF-UPHRSURJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.1
• 重原子数：
  21
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.84
• 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：

  9-十烯-1-醇 在 ruthenium carbene complex 硫酸 作用下， 以 苯 为溶剂， 反应 29.0h， 生成 (Z)-oxacycloicos-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

• Stereoselective Access to <i>Z</i> and <i>E</i> Macrocycles by Ruthenium-Catalyzed <i>Z</i>-Selective Ring-Closing Metathesis and Ethenolysis
  作者：Vanessa M. Marx、Myles B. Herbert、Benjamin K. Keitz、Robert H. Grubbs

  DOI：10.1021/ja311241q

  日期：2013.1.9

  selectivity for Z macrocycles is consistently high for a diverse set of substrates with a variety of functional groups and ring sizes. The same catalyst was also employed for the Z-selective ethenolysis of a mixture of E and Z macrocycles, providing the pure E isomer. Notably, an ethylene pressure of only 1 atm was required. These methodologies were successfully applied to the construction of several olfactory

  描述了使用基于钌的复分解催化剂的 Z 选择性大环化的第一份报告。对于具有各种官能团和环大小的多种底物，Z 大环的选择性始终很高。同样的催化剂也用于 E 和 Z 大环混合物的 Z 选择性乙烯醇解，提供纯 E 异构体。值得注意的是，只需要 1 个大气压的乙烯压力。这些方法已成功应用于几种嗅觉大环化合物的构建以及细胞毒性生物碱莫托泊明 C 的正式全合成。
• Olefin Metathesis in Confined Geometries: A Biomimetic Approach toward Selective Macrocyclization
  作者：Felix Ziegler、Johannes Teske、Iris Elser、Michael Dyballa、Wolfgang Frey、Hamzeh Kraus、Niels Hansen、Julia Rybka、Ulrich Tallarek、Michael R. Buchmeiser

  DOI：10.1021/jacs.9b08776

  日期：2019.12.4

  The synthesis of macrocycles is severely impeded by concomitant oligomer formation. Here, we present a biomimetic approach that utilizes spatial confinement to increase macrocyclization selectivity in the ring clos-ing metathesis of various dienes at elevated substrate concentration up to 25 mM using an olefin me-tathesis catalyst selectively immobilized inside ordered mesoporous silicas with defined

  伴随的低聚物形成严重阻碍了大环化合物的合成。在这里，我们提出了一种仿生方法，该方法利用空间限制来提高底物浓度高达 25 MM 的各种二烯闭环复分解中的大环化选择性，使用烯烃复分解催化剂选择性固定在具有确定孔径的有序介孔二氧化硅内. 通过这种方法，大（单）环化 (MMC) 产物与由无环二烯复分解聚合产生的所有不需要的低聚产物 (O) 之间的比率从 0.55 增加，对应于用均相催化剂获得的 35% MMC 产物，高达 1.49，对应 60% MMC 产品。成功地建立了 MMC/O 比和基材与孔径比之间的相关性。用二甲基二甲氧基硅烷修饰内孔表面可以微调有效孔径并反转表面极性，这导致 MMC/O 比进一步增加至 2.2，对应于 > 68% MMC 产品。模型孔隙几何结构中的分子级模拟有助于使空间限制、特定（基材和产品）与孔隙表面的相互作用以及扩散传输之间复杂的相互作用合理化。这些效果可以通过合适的
• Macrocyclization of Dienes under Confinement with Cationic Tungsten Imido/Oxo Alkylidene <i>N</i>‐Heterocyclic Carbene Complexes
  作者：Felix Ziegler、Johanna R. Bruckner、Michal Nowakowski、Matthias Bauer、Patrick Probst、Boshra Atwi、Michael R. Buchmeiser

  DOI：10.1002/cctc.202300871

  日期：2023.11.8

  Two tungsten-based catalysts have been selectively immobilized within the pores of ordered mesoporous silica materials. X-ray absorption spectroscopy confirm the structural integrity of the catalysts. Compared to the homogenous analogues, the immobilized tungsten-catalysts exhibit a substantially increased macrocyclization- and Z-selectivity, which allow for the use of high substrate concentrations

  两种钨基催化剂被选择性地固定在有序介孔二氧化硅材料的孔内。X 射线吸收光谱证实了催化剂的结构完整性。与同质类似物相比，固定化钨催化剂表现出显着提高的大环化选择性和Z选择性，从而允许使用高底物浓度。
• 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.