(E)-(6R,12R)-6-hydroxy-12-methyloxacyclododec-3-ene-2,5-dione | 1108162-65-7

• 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)-(6R,12R)-6-hydroxy-12-methyloxacyclododec-3-ene-2,5-dione
• 英文别名: (6R,12R,E)-6-hydroxy-12-methyloxacyclododec-3-ene-2,5-dione；(3E,6R,12R)-6-hydroxy-12-methyl-1-oxacyclododec-3-ene-2,5-dione
• CAS: 1108162-65-7
• 化学式: C₁₂H₁₈O₄
• 分子量: 226.273
• InChiKey: OFRQIORIBGXHBF-WENXHQBNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  16
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  63.6
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  (6R,12R,E)-6-(tert-butyldimethylsilyloxy)-12-methyloxacyclododec-3-ene-2,5-dione 在 氢氟酸 作用下， 以 乙腈 为溶剂， 以85%的产率得到(E)-(6R,12R)-6-hydroxy-12-methyloxacyclododec-3-ene-2,5-dione
  参考文献：
  名称：

  从头的不对称合成克拉多普斯B-D：通过对其对映异构体的合成对克拉多普斯D进行结构重新分配

  摘要：

  从1壬炔起11-15步就完成了对克拉多普列B，C和（ent）-克拉多普列D的对映选择性合成。该路线依赖于炔烃拉链反应，将九个碳片段上的炔酮和二烯酸酯官能团进行中继，从而实现高度对映选择性的Noyori炔酮还原，以及二烯酸酯的非对映选择性和区域选择性Sharpless二羟基化反应。除了对克拉多波利斯自然产品的三个成员采取灵活的方法外，这条路线首次正确地建立了克拉多波利斯D的结构。

  DOI：

  10.1021/ol9000119

文献信息

• Structure Investigations of (ent)-Cladospolide D by De Novo Synthesis and Kinetic and Thermodynamic Isomerization
  作者：John Penn、George O’Doherty、Yalan Xing

  DOI：10.1055/s-0029-1217606

  日期：2009.9

  dihydroxylation of a dienoate installed the remaining stereochemistry. The de novo asymmetric route allowed for the asymmetric synthesis of three members of the cladospolide natural products and correctly established the structure for cladospolide D. cladospolides B-D - asymmetric synthesis - natural product synthesis - E/Z-alkene isomerization

  从非手性非1-炔实现了cladospolides B和C和（ent）-cladospolide D的从头不对称合成。11-13步的路线依赖于Noyori还原反应和KAPA促进的炔烃拉链反应，以跨越九个碳原子片段传递非手性官能团并实现二烯酸官能团的安装。二烯酸酯的非对映选择性和区域选择性Sharpless二羟基化反应可保留剩余的立体化学。从头不对称路线允许克拉多波德天然产物的三个成员的不对称合成，并正确建立了克拉多波德D的结构。 cladospolides BD-不对称合成-天然产物合成-E / Z-烯烃异构化
• Synthesis and stereochemical assignment of (+)-Cladospolide D
  作者：Ke-Jhen Lu、Chia-Hsiu Chen、Duen-Ren Hou

  DOI：10.1016/j.tet.2008.10.059

  日期：2009.1

  Cladospolides A-D are 12-membered, alpha,beta-unsaturated lactones isolated from various species of Cladosporium. Cladospolide D is unique in its gamma-keto functionality and possesses antifungal activity; however, the stereochemistry of Cladoapolide D was unknown. We report the asymmetric syntheses to generate both possible diastereomers of Cladospolide D. Two regioselective cross-metatheses were applied to form the carbon skeleton, and the two olefins were differentiated by Michael addition, hydrogenation, and elimination. Later, the macrocycle was achieved through the Yamaguchi protocol. After comparing the spectroscopic data of the synthetic Cladospolide D with the reported values, the stereochemistry of Cladospolide D is confirmed as (2E,5R,11S). (C) 2008 Elsevier Ltd. All rights reserved.
• De Novo Asymmetric Synthesis of Cladospolide B−D: Structural Reassignment of Cladospolide D via the Synthesis of its Enantiomer
  作者：Yalan Xing、George A. O’Doherty

  DOI：10.1021/ol9000119

  日期：2009.3.5

  The enantioselective synthesis of cladospolide B, C, and (ent)-cladospolide D has been achieved in 11−15 steps from 1-nonyne. The route relies upon an alkyne zipper reaction to relay an ynone and dienoate functional groups across a nine carbon fragment, which enables a highly enantioselective Noyori ynone reduction and a diastereo- and regioselective Sharpless dihydroxylation of a dienoate. In addition

  从1壬炔起11-15步就完成了对克拉多普列B，C和（ent）-克拉多普列D的对映选择性合成。该路线依赖于炔烃拉链反应，将九个碳片段上的炔酮和二烯酸酯官能团进行中继，从而实现高度对映选择性的Noyori炔酮还原，以及二烯酸酯的非对映选择性和区域选择性Sharpless二羟基化反应。除了对克拉多波利斯自然产品的三个成员采取灵活的方法外，这条路线首次正确地建立了克拉多波利斯D的结构。