1-(1-l-menthyloxy)-3-(tert-butyldimethylsilyloxy)-1,3-butadiene

• 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: 1-(1-l-menthyloxy)-3-(tert-butyldimethylsilyloxy)-1,3-butadiene
• 英文别名: trimethyl-[(3E)-4-[(1R,2S,5R)-5-methyl-2-propan-2-ylcyclohexyl]oxybuta-1,3-dien-2-yl]oxysilane
• 化学式: C₁₇H₃₂O₂Si
• 分子量: 296.525
• InChiKey: BHJAWVRICGHIAU-RUXMWWCHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.34
• 重原子数：
  20
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.76
• 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：

  3-(tert-butyldiphenylsilyloxy)-1-propanal 、 1-(1-l-menthyloxy)-3-(tert-butyldimethylsilyloxy)-1,3-butadiene 在 Europium tris[3-(CF₃CF₂CF₂CH(O))-(+)-camphorate] 作用下， 以 正己烷 为溶剂， 反应 24.0h， 生成 (-)-(2S)-2-[2-(tert-butyldiphenylsiloxy)ethyl]-2H-pyran-4(3H)-one 、 (+)-(2R)-2-[2-(tert-butyldiphenylsiloxy)ethyl]-2H-pyran-4(3H)-one
  参考文献：
  名称：

  Synthetic studies directed toward the phorboxazoles: preparation of the C3–C15 bisoxane segment and two stereoisomers

  摘要：

  A synthetic approach to the C3-C15 segment of the cytotoxic marine metabolite phorboxazoles is described. This segment consists of a methylene linked bisoxane structure. The first pyran ring was constructed by a Lewis acid catalyzed diene-aldehyde cyclo-condensation. The beta-C-glucoside substitution pattern of this ring was established by a stereoselective allylation. Ozonolysis of vinyl group and enantioselective allylation of the racemic aldehyde generated two separable homoallylic alcohols (-)-22 and (+)-23. The Mosher's esters of each alcohol were determined to be >90% de. Reaction of (-)-22 with acryloyl chloride, followed by ring closing metathesis gave the dihydro-2-pyrone target (-)-5. Mitsunobu inversion of (+)-23 with p-nitrobenzoic acid, hydrolysis, and esterification with acryloyl chloride and ring closing metathesis gave pseudoenantiomeric segment (+)-6. (C) 2002 Published by Elsevier Science Ltd.

  DOI：

  10.1016/s0040-4020(02)00613-0

文献信息

• Rafel, Sara; Cabarrocas, Gemma; Ventura, Montserrat, Journal of the Chemical Society. Perkin transactions I, 1998, # 22, p. 3837 - 3843
  作者：Rafel, Sara、Cabarrocas, Gemma、Ventura, Montserrat、Parella, Teo

  DOI：——

  日期：——
• Heras, Montserrat; Planas, Marta; Rafel, Sara, Anales de Quimica, 1996, vol. 92, # 4, p. 233 - 242
  作者：Heras, Montserrat、Planas, Marta、Rafel, Sara、Ventura, Montserrat、Font, Josep、Ortuno, Rosa M.

  DOI：——

  日期：——
• Poljak, Tanja; Molcanov, Kresimir; Margetic, Davor, Croatica Chemica Acta, 2008, vol. 81, # 4, p. 539 - 558
  作者：Poljak, Tanja、Molcanov, Kresimir、Margetic, Davor、Habus, Ivan

  DOI：——

  日期：——
• Synthetic studies directed toward the phorboxazoles: preparation of the C3–C15 bisoxane segment and two stereoisomers
  作者：Patrick B. Greer、William A. Donaldson

  DOI：10.1016/s0040-4020(02)00613-0

  日期：2002.7

  A synthetic approach to the C3-C15 segment of the cytotoxic marine metabolite phorboxazoles is described. This segment consists of a methylene linked bisoxane structure. The first pyran ring was constructed by a Lewis acid catalyzed diene-aldehyde cyclo-condensation. The beta-C-glucoside substitution pattern of this ring was established by a stereoselective allylation. Ozonolysis of vinyl group and enantioselective allylation of the racemic aldehyde generated two separable homoallylic alcohols (-)-22 and (+)-23. The Mosher's esters of each alcohol were determined to be >90% de. Reaction of (-)-22 with acryloyl chloride, followed by ring closing metathesis gave the dihydro-2-pyrone target (-)-5. Mitsunobu inversion of (+)-23 with p-nitrobenzoic acid, hydrolysis, and esterification with acryloyl chloride and ring closing metathesis gave pseudoenantiomeric segment (+)-6. (C) 2002 Published by Elsevier Science Ltd.