ethyl (2E,4S)-2,4-dimethyl-7-(trimethylsilyl)hept-2-en-6-ynoate | 1359872-29-9

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: ethyl (2E,4S)-2,4-dimethyl-7-(trimethylsilyl)hept-2-en-6-ynoate
• 英文别名: ethyl (E,4S)-2,4-dimethyl-7-trimethylsilylhept-2-en-6-ynoate
• CAS: 1359872-29-9
• 化学式: C₁₄H₂₄O₂Si
• 分子量: 252.429
• InChiKey: MZTJRHQCRZQONO-OWRWYXLESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  17
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.64
• 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：

  ethyl (2E,4S)-2,4-dimethyl-7-(trimethylsilyl)hept-2-en-6-ynoate 在 1,8-双二甲氨基萘 、 二异丁基氢化铝 、 potassium carbonate 、 戴斯-马丁氧化剂 、 (-)-B-methoxydiisopinocampheylborane 作用下， 以 四氢呋喃 、 甲醇 、 乙醚 、 正己烷 、 二氯甲烷 为溶剂， 反应 17.75h， 生成 (1E,4S,5E,7S)-1-iodo-7-methoxy-4,6-dimethyldeca-1,5,9-triene
  参考文献：
  名称：

  Synthesis of the C1-C13 Fragment of Biselyngbyaside

  摘要：

  通过乙烯醇与烯烃构建块之间的交叉复分解反应，制备了对应于大环内酯biselyngbyaside的C1-C13片段的高级中间体乙烯碘化物。含有两个立体中心的后者片段，通过采用不对称烷基化、Wittig反应、氢锆化以及Brown烯丙基化等关键步骤获得。

  DOI：

  10.1055/s-0031-1289898
• 作为产物：
  描述：

  (2S)-2-methyl-5-trimethylsilyl-4-pentyn-1-ol 在 戴斯-马丁氧化剂 作用下， 以 二氯甲烷 为溶剂， 反应 0.92h， 生成 ethyl (2E,4S)-2,4-dimethyl-7-(trimethylsilyl)hept-2-en-6-ynoate
  参考文献：
  名称：

  Convergent Synthesis and Discovery of a Natural Product-Inspired Paralog-Selective Hsp90 Inhibitor

  摘要：

  A convergent synthesis of benzoquinone ansamycin analogs is described that proceeds by a sequence of metallacycle-mediated alkyne-alkyne coupling, followed by site- and stereoselective dihydroxylation and global carbamate formation. These studies have led to (1) validation of alkyne-alkyne coupling to produce geldanamycin analogs that lack the problematic quinone, (2) the discovery that C6-C7 bis-carbamate functionality is compatible with Hsp90 inhibition, and (3) the identification of 1 as a nonquinone geldanamycin-inspired paralog-selective Hsp90 inhibitor.

  DOI：

  10.1021/ol2019828

文献信息

• Synthesis of the C1-C13 Fragment of Biselyngbyaside
  作者：Martin Maier、Pramod Sawant

  DOI：10.1055/s-0031-1289898

  日期：2011.12

  An advanced intermediate vinyl iodide corresponding to the C1-C13 fragment of the macrolide biselyngbyaside was prepared by a cross-metathesis reaction between vinyl alcohol and ­alkene building blocks. The latter fragment, containing two stereocenters, was obtained by employing an asymmetric alkylation, a Wittig reaction, a hydrozirconation, and a Brown allylation as key steps.

  通过乙烯醇与烯烃构建块之间的交叉复分解反应，制备了对应于大环内酯biselyngbyaside的C1-C13片段的高级中间体乙烯碘化物。含有两个立体中心的后者片段，通过采用不对称烷基化、Wittig反应、氢锆化以及Brown烯丙基化等关键步骤获得。
• Convergent Synthesis and Discovery of a Natural Product-Inspired Paralog-Selective Hsp90 Inhibitor
  作者：Valer Jeso、Lisa Cherry、Todd K. Macklin、Subhas Chandra Pan、Philip V. LoGrasso、Glenn C. Micalizio

  DOI：10.1021/ol2019828

  日期：2011.10.7

  A convergent synthesis of benzoquinone ansamycin analogs is described that proceeds by a sequence of metallacycle-mediated alkyne-alkyne coupling, followed by site- and stereoselective dihydroxylation and global carbamate formation. These studies have led to (1) validation of alkyne-alkyne coupling to produce geldanamycin analogs that lack the problematic quinone, (2) the discovery that C6-C7 bis-carbamate functionality is compatible with Hsp90 inhibition, and (3) the identification of 1 as a nonquinone geldanamycin-inspired paralog-selective Hsp90 inhibitor.