(S,E)-ethyl 7-(tert-butyldimethylsilyloxy)-6-hydroxy-2-methylhept-2-enoate | 869732-12-7

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: (S,E)-ethyl 7-(tert-butyldimethylsilyloxy)-6-hydroxy-2-methylhept-2-enoate
• 英文别名: ethyl (E,6S)-7-[tert-butyl(dimethyl)silyl]oxy-6-hydroxy-2-methylhept-2-enoate
• CAS: 869732-12-7
• 化学式: C₁₆H₃₂O₄Si
• 分子量: 316.513
• InChiKey: UVHMEPLOPXPICD-UELRPHRMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.66
• 重原子数：
  21
• 可旋转键数：
  10
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.81
• 拓扑面积：
  55.8
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (S,E)-ethyl 7-(tert-butyldimethylsilyloxy)-6-hydroxy-2-methylhept-2-enoate 在 盐酸 、 乙醇 、 1,8-双二甲氨基萘 作用下， 以 二氯甲烷 为溶剂， 生成 (6S,2E)-ethyl 6-methoxy-2-methyl-7-hydroxyhept-2-enoate
  参考文献：
  名称：

  通过螯合控制的非对映选择性地将二异丙烯基锌添加到α-甲氧基醛中，合成自身霉素的C1–8片段

  摘要：

  自身霉素的C1–8片段是通过可靠的10步路线合成的，该路线能够以克为单位提供41％的总收率。作为关键步骤，使用二异丙烯基锌，卤化镁和二氯甲烷/甲苯混合溶剂的试剂组合建立了α-氧化醛的螯合控制的异丙烯基化。蛤-螯合物异丙烯基化产物主要被具有少量α-取代基的醛所占据，例如–OMe和–OBn基团，而Felkin产物可以通过庞大的–OTBS基团获得。

  DOI：

  10.1016/j.tet.2013.08.067
• 作为产物：
  描述：

  L-谷氨酸 在 咪唑 、 盐酸 、 dimethyl sulfide borane 、 二异丁基氢化铝 、 sodium nitrite 作用下， 以 四氢呋喃 、 N,N-二甲基甲酰胺 、 甲苯 、 苯 为溶剂， 反应 8.0h， 生成 (S,E)-ethyl 7-(tert-butyldimethylsilyloxy)-6-hydroxy-2-methylhept-2-enoate
  参考文献：
  名称：

  Total Synthesis of Reblastatin

  摘要：

  Enantioselective total synthesis of reblastatin is described. The synthesis highlights hydrozirconation, transmetalation, aldehyde addition sequence to install E-trisubstituted olefin and C7 stereocenter, and the first use of an intramolecular Buchwald-like amidation reaction to close the 19-membered macrolactam.

  DOI：

  10.1021/ja055384d

文献信息

• Synthesis of Reblastatin, Autolytimycin, and Non-Benzoquinone Analogues: Potent Inhibitors of Heat Shock Protein 90
  作者：Iwona E. Wrona、Alexander Gozman、Tony Taldone、Gabriela Chiosis、James S. Panek

  DOI：10.1021/jo1000109

  日期：2010.5.7

  A full account of an asymmetric synthesis of reblastatin (1) and the first total synthesis of autolytimycin (2) and related structural compounds is described. The syntheses expand the utility of a highly regio- and diastereoselective hydrometalation aldehyde addition sequence to assemble the fully functionalized ansa chain of the natural products. Also documented is an intramolecular copper-mediated amidation reaction to close the 19-membered macrolactams. The amidation reaction was also employed for the generation of structural derivatives (6-9) of phenolic ansamycins. Ansamycin natural products and selected structural analogues were evaluated in a competitive binding assay to breast cancer cell lysate and a cytotoxicity assay. Both reblastatin (1) and autolytimycin (2) were shown to bind the heat shock protein 90 with enhanced binding activity (similar to 25 nM) than 17-allylamino-17-demethoxygeldanamycin (17-AAG, 4), a geldanamycin (3) derivative currently under evaluation for treatment of cancer (similar to 100 nM).
• Total Synthesis of Reblastatin
  作者：Iwona E. Wrona、Ana E. Gabarda、Gwilherm Evano、James S. Panek

  DOI：10.1021/ja055384d

  日期：2005.11.1

  Enantioselective total synthesis of reblastatin is described. The synthesis highlights hydrozirconation, transmetalation, aldehyde addition sequence to install E-trisubstituted olefin and C7 stereocenter, and the first use of an intramolecular Buchwald-like amidation reaction to close the 19-membered macrolactam.
• Practical synthesis of C1–8 fragment of autolytimycin via a chelation-controlled diastereoselective addition of diisopropenylzinc to α-methoxy aldehyde
  作者：Fan Yang、Liang Feng、Nengzhong Wang、Xuge Liu、Jun Li、Yuehai Shen

  DOI：10.1016/j.tet.2013.08.067

  日期：2013.11

  capable of delivering 41% overall yield at multi-gram scale. As a key step, a chelation-controlled isopropenylation of α-oxygenated aldehydes was established with a reagent combination of diisopropenylzinc, magnesium halide, and a dichloromethane/toluene mixed solvent. Cram-chelate isopropenylation products dominated for aldehydes with a small α-substituents, such as –OMe and –OBn groups, while the Felkin

  自身霉素的C1–8片段是通过可靠的10步路线合成的，该路线能够以克为单位提供41％的总收率。作为关键步骤，使用二异丙烯基锌，卤化镁和二氯甲烷/甲苯混合溶剂的试剂组合建立了α-氧化醛的螯合控制的异丙烯基化。蛤-螯合物异丙烯基化产物主要被具有少量α-取代基的醛所占据，例如–OMe和–OBn基团，而Felkin产物可以通过庞大的–OTBS基团获得。