ethyl (2E,5S,6R,7E)-5-{[(tert-butyl)dimethylsilyl]oxy}-6-methyl-8-phenylocta-2,7-dienoate

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: ethyl (2E,5S,6R,7E)-5-{[(tert-butyl)dimethylsilyl]oxy}-6-methyl-8-phenylocta-2,7-dienoate
• 英文别名: (2E,5S,6R,7E)-ethyl 5-(tert-butyldimethylsilyloxy)-6-methyl-8-phenylocta-2,7-dienoate；ethyl (2E,5S,6R,7E)-5-[tert-butyl(dimethyl)silyl]oxy-6-methyl-8-phenylocta-2,7-dienoate
• 化学式: C₂₃H₃₆O₃Si
• 分子量: 388.623
• InChiKey: BKFJOEJPYGMYJO-ZXMZNTBJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.24
• 重原子数：
  27
• 可旋转键数：
  11
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.52
• 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：

  ethyl (2E,5S,6R,7E)-5-{[(tert-butyl)dimethylsilyl]oxy}-6-methyl-8-phenylocta-2,7-dienoate 在 tetra-n-butylammoniumfluoride trihydrate 作用下， 以 四氢呋喃 为溶剂， 反应 4.0h， 以74%的产率得到(2E,5S,6R,7E)-ethyl 5-hydroxy-6-methyl-8-phenylocta-2,7-dienoate
  参考文献：
  名称：

  A cyclopropanol-based approach to synthesis of Unit A of the cryptophycins

  摘要：

  A new asymmetric synthesis of Unit A of the cryptophycins has been carried out yielding 13% of the target product over 14 steps. The key steps of the synthesis were diastereoselective hydroboration-oxidation reactions performed on the alkenyl moiety of a 1,3-dioxane derivative 8, which can be easily prepared via the Kulinkovich cyclopropanation of protected diethyl (S)-(-)-malate followed by transformation of the resulting small rings of the product 6 into the functional groups necessary for the synthesis of the target compound. (C) 2014 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2014.03.011
• 作为产物：
  描述：

  (S)-5,5-dimethyl-7-((R,E)-4-phenylbut-3-en-2-yl)-4,6-dioxaspiro[2.5]octane 在 咪唑 、 4-甲基苯磺酸吡啶 、 sodium hydride 、 二异丁基氢化铝 作用下， 以 四氢呋喃 、 N,N-二甲基甲酰胺 、 甲苯 、 mineral oil 为溶剂， 反应 4.83h， 生成 ethyl (2E,5S,6R,7E)-5-{[(tert-butyl)dimethylsilyl]oxy}-6-methyl-8-phenylocta-2,7-dienoate
  参考文献：
  名称：

  A cyclopropanol-based approach to synthesis of Unit A of the cryptophycins

  摘要：

  A new asymmetric synthesis of Unit A of the cryptophycins has been carried out yielding 13% of the target product over 14 steps. The key steps of the synthesis were diastereoselective hydroboration-oxidation reactions performed on the alkenyl moiety of a 1,3-dioxane derivative 8, which can be easily prepared via the Kulinkovich cyclopropanation of protected diethyl (S)-(-)-malate followed by transformation of the resulting small rings of the product 6 into the functional groups necessary for the synthesis of the target compound. (C) 2014 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2014.03.011

文献信息

• Flexible Routes to the 5-Hydroxy Acid Fragment of the Cryptophycins
  作者：Prodeep Phukan、Sanjita Sasmal、Martin E. Maier

  DOI：10.1002/ejoc.200210695

  日期：2003.5

  Two solutions to establishing the anti stereochemistry of the vicinal stereocenters in the 5-hydroxy acid subunit of cryptophycin, based on initial Evans syn aldol reactions between an N-(propionyl)oxazolidinone 4 and a C3 aldehyde, were developed. In the first route, the secondary hydroxy group was inverted by use of Mitsunobu reaction conditions, whereas the second route features an inversion of

  基于 N-（丙酰基）恶唑烷酮 4 和 C3 醛之间的初始 Evans Syn aldol 反应，开发了两种解决方案，用于建立 cryptophycin 的 5-羟基酸亚基中的邻位立体中心的反立体化学。在第一条路线中，仲羟基通过使用光信反应条件反转，而第二条路线的特点是带有甲基的立体中心的反转，通过手性助剂的还原去除、消除得到末端烯烃和反-选择性硼氢化。芳基部分可以通过 Wittig-Horner 烯化或修饰的 Julia 偶联连接。两条路线都以非常有效的方式提供羟基酸16。硼氢化的底物烯烃 22 也可以从 (S)-苹果酸获得。(© Wiley-VCH Verlag GmbH & Co.