(3aR,4S,6aR,8S,9aR,9bR)-8-((tert-butyldimethylsilyl)oxy)-3,6,9-trimethylene-2-oxododecahydroazuleno[4,5-b]furan-4-yl 2-(((tert-butyldimethylsilyl)oxy)methyl)acrylate | 142138-69-0

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: (3aR,4S,6aR,8S,9aR,9bR)-8-((tert-butyldimethylsilyl)oxy)-3,6,9-trimethylene-2-oxododecahydroazuleno[4,5-b]furan-4-yl 2-(((tert-butyldimethylsilyl)oxy)methyl)acrylate
• 英文别名: 3,3'-bis-O-(tert-butyldimethylsilyl)cynaropicrin；[(3aR,4S,6aR,8S,9aR,9bR)-8-[tert-butyl(dimethyl)silyl]oxy-3,6,9-trimethylidene-2-oxo-3a,4,5,6a,7,8,9a,9b-octahydroazuleno[4,5-b]furan-4-yl] 2-[[tert-butyl(dimethyl)silyl]oxymethyl]prop-2-enoate
• CAS: 142138-69-0；148320-25-6
• 化学式: C₃₁H₅₀O₆Si₂
• 分子量: 574.905
• InChiKey: YEBOBHPSYSODMX-DYIJDPQUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.12
• 重原子数：
  39
• 可旋转键数：
  10
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.68
• 拓扑面积：
  71.1
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  (3aR,4S,6aR,8S,9aR,9bR)-8-((tert-butyldimethylsilyl)oxy)-3,6,9-trimethylene-2-oxododecahydroazuleno[4,5-b]furan-4-yl 2-(((tert-butyldimethylsilyl)oxy)methyl)acrylate 在 对甲苯磺酸 sodium tetrahydroborate 、 氧气 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 9.5h， 生成 3,3'-bis-O-(tert-butyldimethylsilyl)-13-(1'-hydroxyethyl)-16-(2''-(tetrahydropyranyl)oxy)-11α-hydroxy-11,13-dihydrocynaropicrin
  参考文献：
  名称：

  两种天然存在的氧杂环丁烷内酯的首次合成：克莱门汀和克莱门汀b

  摘要：

  从α，β-不饱和的γ-内酯γ-内酯芥子油苷（6）合成了Clementein（1）和ClementeinB（2），具有从Centaurea clementei Boiss分离的具有11,13-氧杂环丁烷环的倍半萜烯内酯。在该转化中已采用共轭光加成，立体选择性α-羟基化和温和环化以使用THP作为离去基团形成氧杂环丁烷环。

  DOI：

  10.1016/s0040-4020(01)86328-6
• 作为产物：
  描述：

  (3aR,4S,6aR,8S,9aR,9bR)-8-((tert-butyldimethylsilyl)oxy)-3,6,9-trimethylene-2-oxododecahydroazuleno[4,5-b]furan-4-yl 2-(((triisopropylsilyl)oxy)methyl)acrylate 在 2,4,6-三甲基吡啶 、 四丁基氟化铵 作用下， 以 四氢呋喃 、 N,N-二甲基甲酰胺 为溶剂， 反应 7.0h， 生成 (3aR,4S,6aR,8S,9aR,9bR)-8-((tert-butyldimethylsilyl)oxy)-3,6,9-trimethylene-2-oxododecahydroazuleno[4,5-b]furan-4-yl 2-(((tert-butyldimethylsilyl)oxy)methyl)acrylate
  参考文献：
  名称：

  Synthesis of cynaropicrin- d 4

  摘要：

  Cynaropicrin is a guaianolide sesquiterpene lactone, which has potent in vitro and in vivo inhibitory activity against Trypanosoma brucei, the protozoan parasite that causes human African trypanosomiasis (HAT; sleeping sickness). Herein, we describe the synthesis of cynaropicrin's deuterated derivative, cynaropicrin-d(4), by the replacement of the side chain of natural cynaropicrin. The synthesized cynaropicrin-d(4) could be employed as an internal standard for liquid chromatography-mass spectrometry (LC-MS) analysis, in the pharmacokinetic study of cynaropicrin. This could potentially advance the study of this therapeutic lead. (C) 2015 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.bmcl.2015.10.065

文献信息

• Study of photochemical addition of acyl radical to electron-deficient olefins
  作者：Francisco A. Macías、José María G. Molinillo、Guillermo M. Massanet、Francisco Rodríguez-Luis

  DOI：10.1016/0040-4020(92)85010-c

  日期：1992.1

  The photochemical addition of acyl radical to electron-deficient olefins is studied. The scope of the reaction, the mechanism, the role that molecular oxygen plays, the influence of steric effects, and the side reaction that take place are discussed. The reaction was carried out using a range of electron-withdrawing substituents (ketones, amides, lactones, nitrile and esters) with good yields of the

  研究了酰基向光电子不足的烯烃的光化学加成。讨论了反应的范围，机理，分子氧的作用，空间效应的影响以及发生的副反应。在所有情况下，使用一定范围的吸电子取代基（酮，酰胺，内酯，腈和酯）进行反应，并得到相应的光加合物。
• Synthesis of cynaropicrin- d 4
  作者：Takuya Sato、Shihori Hara、Makiko Sato、Keita Ogawa、Michael Adams、Toyonobu Usuki

  DOI：10.1016/j.bmcl.2015.10.065

  日期：2015.12

  Cynaropicrin is a guaianolide sesquiterpene lactone, which has potent in vitro and in vivo inhibitory activity against Trypanosoma brucei, the protozoan parasite that causes human African trypanosomiasis (HAT; sleeping sickness). Herein, we describe the synthesis of cynaropicrin's deuterated derivative, cynaropicrin-d(4), by the replacement of the side chain of natural cynaropicrin. The synthesized cynaropicrin-d(4) could be employed as an internal standard for liquid chromatography-mass spectrometry (LC-MS) analysis, in the pharmacokinetic study of cynaropicrin. This could potentially advance the study of this therapeutic lead. (C) 2015 Elsevier Ltd. All rights reserved.
• First synthesis of two naturally occurring oxetane lactones: clementein and clementein b
  作者：Francisco A. Macías、José María G. Molinillo、Guillermo M. Massanet

  DOI：10.1016/s0040-4020(01)86328-6

  日期：1993.3

  Clementein (1) and clementein B (2), sesquiterpene lactones with an 11,13-oxetane ring isolated from Centaurea clementei Boiss, have been synthesized from the α, β-unsaturated γ-lactone cynaropicrin (6). Conjugated photoaddition, stereoselective α-hydroxylation and mild cyclization to form the oxetane ring using THP as leaving group have been employed in this transformation.

  从α，β-不饱和的γ-内酯γ-内酯芥子油苷（6）合成了Clementein（1）和ClementeinB（2），具有从Centaurea clementei Boiss分离的具有11,13-氧杂环丁烷环的倍半萜烯内酯。在该转化中已采用共轭光加成，立体选择性α-羟基化和温和环化以使用THP作为离去基团形成氧杂环丁烷环。