2,2-dimethylpropionic acid (4R,5S,6S)-2,4,6-trimethyl-5-(triethylsilanyloxy)-non-2-trans-en-8-ynyl ester | 381246-98-6

• 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: 2,2-dimethylpropionic acid (4R,5S,6S)-2,4,6-trimethyl-5-(triethylsilanyloxy)-non-2-trans-en-8-ynyl ester
• 英文别名: [(E,4R,5S,6S)-2,4,6-trimethyl-5-triethylsilyloxynon-2-en-8-ynyl] 2,2-dimethylpropanoate
• CAS: 381246-98-6
• 化学式: C₂₃H₄₂O₃Si
• 分子量: 394.67
• InChiKey: JMDHOLPLDKNJKN-PVSFNNIRSA-N

物化性质

• 沸点：
  426.0±45.0 °C(Predicted)
• 密度：
  0.913±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.21
• 重原子数：
  27
• 可旋转键数：
  13
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2,2-dimethylpropionic acid (4R,5S,6S)-2,4,6-trimethyl-5-(triethylsilanyloxy)-non-2-trans-en-8-ynyl ester 在 (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride 、 水 manganese(IV) oxide 、 氢氧化钾 、 二氯二茂锆 、 三苯胂 、 四丁基氟化铵 、 二异丁基氢化铝 、 溶剂黄146 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 三乙胺 、 N,N-二异丙基乙胺 、 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 、 1,4-二氧六环 、 正己烷 、 二氯甲烷 、 N,N-二甲基甲酰胺 、 甲苯 为溶剂， 反应 25.17h， 生成 (2Z,4E,6R,7S,8S,10E,12E,14S,15R,16S,17R,18S)-18-[2-[(2R,3S,4R)-2,4-bis[[tert-butyl(dimethyl)silyl]oxy]-3,5-dimethylhexyl]-1,3-dithian-2-yl]-7,15,17-trihydroxy-2,14-dimethoxy-4,6,8,10,16-pentamethylnonadeca-2,4,10,12-tetraenoic acid
  参考文献：
  名称：

  Total Synthesis of Bafilomycin A₁ Relying on Iterative 1,2-Induction in Acyclic Precursors

  摘要：

  The macrolide bafilomycin A(1) was synthesized starting from D-valine and D-mannitol as chiral progenitors of propionate units. Acyclic subunits corresponding to different parts of the molecule were constructed based on an iterative 1,2-asymmetric induction protocol as a distinctive feature of the synthesis. The assembly of two segments encompassing the entire carbon framework of the macrolide was achieved by using a Stille coupling. The resulting seco-ester was further manipulated to provide crystalline bafilomycin A(1) via a conventional carbodiimide-mediated Keck-type macrolactonization.

  DOI：

  10.1021/ja011452u
• 作为产物：
  描述：

  2,2-dimethylpropionic acid (4R,5S,6S)-8-methoxymethoxy-2,4,6-trimethyl-5-(triethylsilanyloxy)-oct-2-trans-enyl ester 在 B-溴代邻苯二氧硼烷 、 potassium carbonate 、 戴斯-马丁氧化剂 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 5.0h， 生成 2,2-dimethylpropionic acid (4R,5S,6S)-2,4,6-trimethyl-5-(triethylsilanyloxy)-non-2-trans-en-8-ynyl ester
  参考文献：
  名称：

  Total Synthesis of Bafilomycin A₁ Relying on Iterative 1,2-Induction in Acyclic Precursors

  摘要：

  The macrolide bafilomycin A(1) was synthesized starting from D-valine and D-mannitol as chiral progenitors of propionate units. Acyclic subunits corresponding to different parts of the molecule were constructed based on an iterative 1,2-asymmetric induction protocol as a distinctive feature of the synthesis. The assembly of two segments encompassing the entire carbon framework of the macrolide was achieved by using a Stille coupling. The resulting seco-ester was further manipulated to provide crystalline bafilomycin A(1) via a conventional carbodiimide-mediated Keck-type macrolactonization.

  DOI：

  10.1021/ja011452u