triisopropylsilyl 3-butynoate | 194807-80-2

• 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: triisopropylsilyl 3-butynoate
• 英文别名: Tri(propan-2-yl)silyl but-3-ynoate
• CAS: 194807-80-2
• 化学式: C₁₃H₂₄O₂Si
• 分子量: 240.418
• InChiKey: GNIPCLONCGWYEJ-UHFFFAOYSA-N

物化性质

• 沸点：
  248.6±23.0 °C(Predicted)
• 密度：
  0.899±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.73
• 重原子数：
  16
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.77
• 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：

  triisopropylsilyl 3-butynoate 在 吡啶 、 Schwartz's reagent 、 三氟乙酸酐 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 3.67h， 生成 triisopropylsilyl 7-cyclohexylhepta-2E,4E,6E-trienoate
  参考文献：
  名称：

  Total Synthesis of (±)-Nisamycin

  摘要：

  We have developed a highly convergent synthesis of the manumycin-type m-C7N-antibiotic nisamycin that is applicable to other members of this family of antibiotics. The synthesis features a three-step sequence to the epoxyquinol core that serves as a scaffold for the attachment of the polyene side chains. The eastern polyene side chain was constructed via a novel organozirconocene-mediated synthesis. Zirconocene methodology was also applied to the synthesis of the polyene side chains of asukamycin. The southern side chain of nisamycin was introduced via a Stille reaction that employed a vinyl bromo ketone, derived from an acid-sensitive bromo ketal. Pd-mediated coupling of the vinyl bromide with a stannyl TIPS ester gave TIPS-protected nisamycin that was readily converted to the natural product.

  DOI：

  10.1021/jo990413m
• 作为产物：
  描述：

  三异丙基氯硅烷 、 3-丁炔酸 在 咪唑 作用下， 以 二氯甲烷 为溶剂， 以95%的产率得到triisopropylsilyl 3-butynoate
  参考文献：
  名称：

  Organozirconocene-mediated polyene synthesis: Preparation of asukamycin and manumycin a side chains

  摘要：

  Hydrozirconation of a functionalized alkyne followed by transmetalation and 1,2-addition to alpha,beta-unsaturated aldehydes was used for the syntheses of the eastern side chain of asukamycin and a precursor to the southern side chain common to asukamycin and manumycin A. These routes facilitate analog preparation, and the convergent zirconocene strategy represents an alternative to stepwise Wittig condensations or Stille couplings in polyene synthesis. (C) 1997 Elsevier Science Ltd.

  DOI：

  10.1016/s0040-4039(97)01129-5

文献信息

• Organozirconocene-mediated polyene synthesis: Preparation of asukamycin and manumycin a side chains
  作者：Peter Wipf、Philip D.G. Coish

  DOI：10.1016/s0040-4039(97)01129-5

  日期：1997.7

  Hydrozirconation of a functionalized alkyne followed by transmetalation and 1,2-addition to alpha,beta-unsaturated aldehydes was used for the syntheses of the eastern side chain of asukamycin and a precursor to the southern side chain common to asukamycin and manumycin A. These routes facilitate analog preparation, and the convergent zirconocene strategy represents an alternative to stepwise Wittig condensations or Stille couplings in polyene synthesis. (C) 1997 Elsevier Science Ltd.
• Total Synthesis of (±)-Nisamycin
  作者：Peter Wipf、Philip D. G. Coish

  DOI：10.1021/jo990413m

  日期：1999.7.1

  We have developed a highly convergent synthesis of the manumycin-type m-C7N-antibiotic nisamycin that is applicable to other members of this family of antibiotics. The synthesis features a three-step sequence to the epoxyquinol core that serves as a scaffold for the attachment of the polyene side chains. The eastern polyene side chain was constructed via a novel organozirconocene-mediated synthesis. Zirconocene methodology was also applied to the synthesis of the polyene side chains of asukamycin. The southern side chain of nisamycin was introduced via a Stille reaction that employed a vinyl bromo ketone, derived from an acid-sensitive bromo ketal. Pd-mediated coupling of the vinyl bromide with a stannyl TIPS ester gave TIPS-protected nisamycin that was readily converted to the natural product.