2-[(3S)-2,3-dimethylpent-4-yn-2-yl]oxyoxane | 1246949-35-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧烷类
• 英文名称: 2-[(3S)-2,3-dimethylpent-4-yn-2-yl]oxyoxane
• CAS: 1246949-35-8
• 化学式: C₁₂H₂₀O₂
• 分子量: 196.29
• InChiKey: PBUNVOGCOOIKNN-VUWPPUDQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  14
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2-[(3S)-2,3-dimethylpent-4-yn-2-yl]oxyoxane 在 正丁基锂 、 水 、 mercuric triflate 作用下， 以 四氢呋喃 、 正己烷 、 乙腈 为溶剂， 反应 3.17h， 生成 (3α,5α,11β,17ξ,22S,24S)-3,11-bis(benzyloxy)-24-methyl-22,25-epoxyfurostan-20-ol
  参考文献：
  名称：

  Synthesis of the Antiproliferative Agent Hippuristanol and Its Analogues via Suárez Cyclizations and Hg(II)-Catalyzed Spiroketalizations

  摘要：

  A full account of the synthesis of hippuristanol and its analogues is described. Hecogenin acetate was identified as a suitable and economical starting material for this work, and substrate-controlled stereo-selection was obtained throughout the construction of the key spiroketal unit. Suarez cyclization was first used, but Hg(II)-catalyzed spiroketalization of the 3-alkyne-1,7-diol motif was finally identified as the most convenient strategy.

  DOI：

  10.1021/jo102054r
• 作为产物：
  描述：

  (2S)-2,3-二甲基-1,3-丁二醇 在 重铬酸吡啶 、 正丁基锂 、 对甲苯磺酸 作用下， 以 二氯甲烷 为溶剂， 生成 2-[(3S)-2,3-dimethylpent-4-yn-2-yl]oxyoxane
  参考文献：
  名称：

  Synthesis of the Antiproliferative Agent Hippuristanol and Its Analogues via Suárez Cyclizations and Hg(II)-Catalyzed Spiroketalizations

  摘要：

  A full account of the synthesis of hippuristanol and its analogues is described. Hecogenin acetate was identified as a suitable and economical starting material for this work, and substrate-controlled stereo-selection was obtained throughout the construction of the key spiroketal unit. Suarez cyclization was first used, but Hg(II)-catalyzed spiroketalization of the 3-alkyne-1,7-diol motif was finally identified as the most convenient strategy.

  DOI：

  10.1021/jo102054r

文献信息

• Synthesis of the Antiproliferative Agent Hippuristanol and Its Analogues from Hydrocortisone via Hg(II)-Catalyzed Spiroketalization: Structure–Activity Relationship
  作者：Ragam Somaiah、Kontham Ravindar、Regina Cencic、Jerry Pelletier、Pierre Deslongchamps

  DOI：10.1021/jm401799j

  日期：2014.3.27

  functional groups on rings A and E. Each analogue was screened for their effects on inhibition of cap-dependent translation, and the assay results were used to establish structure–activity relationships. These results suggest that the stereochemistry and all substituents of spiroketal portion (rings E and F) and C3-α and C11-β hydroxyl functional groups on rings A and C, respectively, are critical for

  有效的合成马尿嘌呤醇（1），一种海洋来源的强效抗增殖甾体天然产物，以及九种紧密相关的类似物，是利用Hg（II）催化3-炔基1,7-的螺酮缩合从市售氢化可的松中完成的。二醇基序作为关键策略。此实际合成顺序布置1中11％的总收率在15级线性从氢化可的松。对母体分子1的修饰包括改变环A和E上的官能团。筛选每种类似物对抑制帽依赖性翻译的影响，并将测定结果用于建立结构与活性的关系。这些结果表明，螺环部分（环E和F）以及环A和C上的C3-α和C11-β羟基官能团的立体化学和所有取代基对于天然产物1的抑制活性至关重要。
• Efficient Synthetic Approach to Potent Antiproliferative Agent Hippuristanol via Hg(II)-Catalyzed Spiroketalization
  作者：Kontham Ravindar、Maddi Sridhar Reddy、Lisa Lindqvist、Jerry Pelletier、Pierre Deslongchamps

  DOI：10.1021/ol1019663

  日期：2010.10.1

  The steroidal natural product hippuristanol targets eukaryotic translation initiation factor (eIF)4A which plays a pivotal role in translation in eukaryotic cells. Now an efficient synthesis of hippuristanol from 11-ketotigogenin is reported. The synthesis features a rapid construction of a spiroketal unit via Hg(OTf)2-catalyzed oxidation/spiroketalization of the 3-alkyn-1,7-diol motif.

  类固醇天然产物hippuristanol靶向真核翻译起始因子（eIF）4A，该因子在真核细胞的翻译中起关键作用。现在已经报道了由11-酮基生成素有效合成马尿嘌呤醇。该合成的特征是通过Hg（OTf）2催化3-炔基1,7-二醇基序的氧化/螺缩酮化作用来快速构建螺缩酮单元。