(4Z)-5,8-bis(trimethylsilanyl)-oct-4-en-7-yn-1-ol | 560107-94-0

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: (4Z)-5,8-bis(trimethylsilanyl)-oct-4-en-7-yn-1-ol
• 英文别名: (Z)-5,8-bis(trimethylsilyl)oct-4-en-7-yn-1-ol
• CAS: 560107-94-0
• 化学式: C₁₄H₂₈OSi₂
• 分子量: 268.547
• InChiKey: OUTCZOZAFPVHIR-UVTDQMKNSA-N

物化性质

• 沸点：
  316.1±42.0 °C(Predicted)
• 密度：
  0.879±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.83
• 重原子数：
  17
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (4Z)-5,8-bis(trimethylsilanyl)-oct-4-en-7-yn-1-ol 在 二异丁基氢化铝 作用下， 以 乙醚 、 正己烷 为溶剂， 反应 46.25h， 生成 (4Z,7Z)-5,8-bis-trimethylsilanyl-nona-4,7-dien-1-ol
  参考文献：
  名称：

  Ladder Polyether Synthesis via Epoxide-Opening Cascades Using a Disappearing Directing Group

  摘要：

  The combination of a trimethylsilyl group, a Brønsted base, a fluoride source, and a hydroxylic solvent enables the first construction of the tetrad of tetrahydropyran rings found in the majority of the ladder polyether natural products by way of a cascade of epoxide-opening events that emulates the final step of Nakanishi's proposed biosynthetic pathway. The trimethylsilyl group disappears during the course of the cascade, and thus these are the first epoxide ring-opening cascades that afford ladder polyether subunits containing no directing groups at the end of the cascade.

  DOI：

  10.1021/ja057973p
• 作为产物：
  描述：

  5-(三甲基硅烷基)-4-戊炔-1-醇 在 正丁基锂 、 四甲基乙二胺 、 二异丁基氢化铝 作用下， 以 四氢呋喃 、 乙醚 、 正己烷 为溶剂， 反应 27.25h， 生成 (4Z)-5,8-bis(trimethylsilanyl)-oct-4-en-7-yn-1-ol
  参考文献：
  名称：

  SiMe₃-Based Homologation−Epoxidation−Cyclization Strategy for Ladder THP Synthesis

  摘要：

  [GRAPHICS]A trimethylsilyl (SiMe3) group is the basis of a strategy that emulates the three fundamental proposed processes in ladder polyether biosynthesis: chain homologation, stereoselective epoxidation (>95% ee or >95:5 dr), and endo-selective, stereospecific (inversion) hydroxyepoxide cyclization (>95:5 endo:exo, >95% dr). A tris-THP was synthesized in 18 total operations from commercial materials using this approach.

  DOI：

  10.1021/ol0347040

文献信息

• Ladder Polyether Synthesis via Epoxide-Opening Cascades Directed by a Disappearing Trimethylsilyl Group
  作者：Timothy P. Heffron、Graham L. Simpson、Estibaliz Merino、Timothy F. Jamison

  DOI：10.1021/jo1002455

  日期：2010.4.16

  Epoxide-opening cascades offer the potential to construct complex polyether natural products expeditiously and in a manner that emulates the biogenesis proposed for these compounds. Herein we provide a full account of our development of a strategy that addresses several important challenges of such cascades. The centerpiece of the method is a trimethylsilyl (SiMe3) group that serves several purposes and leaves no trace of itself by the time the cascade has come to an end. The main function of the SiMe3 group is to dictate the regioselectivity of epoxide opening. This strategy is the only general method of effecting endo-selective cascades under basic conditions.
• SiMe₃-Based Homologation−Epoxidation−Cyclization Strategy for Ladder THP Synthesis
  作者：Timothy P. Heffron、Timothy F. Jamison

  DOI：10.1021/ol0347040

  日期：2003.6.1

  [GRAPHICS]A trimethylsilyl (SiMe3) group is the basis of a strategy that emulates the three fundamental proposed processes in ladder polyether biosynthesis: chain homologation, stereoselective epoxidation (>95% ee or >95:5 dr), and endo-selective, stereospecific (inversion) hydroxyepoxide cyclization (>95:5 endo:exo, >95% dr). A tris-THP was synthesized in 18 total operations from commercial materials using this approach.
• Ladder Polyether Synthesis via Epoxide-Opening Cascades Using a Disappearing Directing Group
  作者：Graham L. Simpson、Timothy P. Heffron、Estíbaliz Merino、Timothy F. Jamison

  DOI：10.1021/ja057973p

  日期：2006.2.1

  The combination of a trimethylsilyl group, a Brønsted base, a fluoride source, and a hydroxylic solvent enables the first construction of the tetrad of tetrahydropyran rings found in the majority of the ladder polyether natural products by way of a cascade of epoxide-opening events that emulates the final step of Nakanishi's proposed biosynthetic pathway. The trimethylsilyl group disappears during the course of the cascade, and thus these are the first epoxide ring-opening cascades that afford ladder polyether subunits containing no directing groups at the end of the cascade.