(2'R,3'S,4'R,5'R)-6'-(tert-butyldimethylsiloxy)-2',4'-dimethyl-5'-methoxy-1'-penten-3'-yl propionate

• 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: (2'R,3'S,4'R,5'R)-6'-(tert-butyldimethylsiloxy)-2',4'-dimethyl-5'-methoxy-1'-penten-3'-yl propionate
• 英文别名: [(3R,4S,5R,6R)-6-[tert-butyl(dimethyl)silyl]oxy-5-methoxy-2,4-dimethylhept-1-en-3-yl] propanoate
• 化学式: C₁₉H₃₈O₄Si
• 分子量: 358.594
• InChiKey: RZGFLOXOBYXFIB-CIRFHOKZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.95
• 重原子数：
  24
• 可旋转键数：
  11
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.84
• 拓扑面积：
  44.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (2'R,3'S,4'R,5'R)-6'-(tert-butyldimethylsiloxy)-2',4'-dimethyl-5'-methoxy-1'-penten-3'-yl propionate 在 六甲基磷酰三胺 、 正丁基锂 、 二异丙胺 、 叔丁基二甲基氯硅烷 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 7.91h， 以75%的产率得到(2R,6S,7R,8R,4E)-8-(tert-butyldimethylsiloxy)-7-methoxy-2,4,6-trimethyl-4-nonenoic acid
  参考文献：
  名称：

  A Total Synthesis of Herboxidiene Methyl Ester

  摘要：

  The total synthesis of the methyl ester, 35, of herboxidiene (1, a.k.a. GEX1A and TAN-1609), a polyketide displaying both herbicidal and anti-tumor activity, is described. The convergent reaction sequence involves, in its closing stages, the union of the phosphine oxide 3 with the aldehyde 21 to deliver, via a Horner-Wittig reaction with accompanying epimerization at C12, compound 33 that after deprotection affords an alcohol, 34, capable of participating in a regio- and diastereo-selective epoxidation reaction to give target 35. Phosphine oxide 3 was prepared via the intramolecular hetero-Michael addition of a secondary alcohol to a tethered and Z-configured acrylate while aldehyde 21 was generated, in the crucial step of the relevant reaction sequence, via an Ireland-Claisen rearrangement reaction.

  DOI：

  10.3987/com-12-12597
• 作为产物：
  描述：

  (2R,3R,4R)-4-(tert-butyldimethylsiloxy)-3-methoxy-2-methylpentanal 在 吡啶 、 4-二甲氨基吡啶 、 叔丁基锂 作用下， 以 乙醚 、 正戊烷 为溶剂， 反应 17.75h， 生成 (2'R,3'S,4'R,5'R)-6'-(tert-butyldimethylsiloxy)-2',4'-dimethyl-5'-methoxy-1'-penten-3'-yl propionate
  参考文献：
  名称：

  A Total Synthesis of Herboxidiene Methyl Ester

  摘要：

  The total synthesis of the methyl ester, 35, of herboxidiene (1, a.k.a. GEX1A and TAN-1609), a polyketide displaying both herbicidal and anti-tumor activity, is described. The convergent reaction sequence involves, in its closing stages, the union of the phosphine oxide 3 with the aldehyde 21 to deliver, via a Horner-Wittig reaction with accompanying epimerization at C12, compound 33 that after deprotection affords an alcohol, 34, capable of participating in a regio- and diastereo-selective epoxidation reaction to give target 35. Phosphine oxide 3 was prepared via the intramolecular hetero-Michael addition of a secondary alcohol to a tethered and Z-configured acrylate while aldehyde 21 was generated, in the crucial step of the relevant reaction sequence, via an Ireland-Claisen rearrangement reaction.

  DOI：

  10.3987/com-12-12597

文献信息

• A Total Synthesis of Herboxidiene Methyl Ester
  作者：Martin G. Banwell、Rajaratnam Premraj、Malcolm D. McLeod、Gregory W. Simpson

  DOI：10.3987/com-12-12597

  日期：——

  The total synthesis of the methyl ester, 35, of herboxidiene (1, a.k.a. GEX1A and TAN-1609), a polyketide displaying both herbicidal and anti-tumor activity, is described. The convergent reaction sequence involves, in its closing stages, the union of the phosphine oxide 3 with the aldehyde 21 to deliver, via a Horner-Wittig reaction with accompanying epimerization at C12, compound 33 that after deprotection affords an alcohol, 34, capable of participating in a regio- and diastereo-selective epoxidation reaction to give target 35. Phosphine oxide 3 was prepared via the intramolecular hetero-Michael addition of a secondary alcohol to a tethered and Z-configured acrylate while aldehyde 21 was generated, in the crucial step of the relevant reaction sequence, via an Ireland-Claisen rearrangement reaction.