(2S,3R,4S,5S)-3-(t-butyldimethylsilyloxy)-2,4-dimethyl-7-oxo-heptan-5-olide | 201054-28-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 内酯类
• 英文名称: (2S,3R,4S,5S)-3-(t-butyldimethylsilyloxy)-2,4-dimethyl-7-oxo-heptan-5-olide
• 英文别名: 2-[(2S,3S,4S,5R)-4-[tert-butyl(dimethyl)silyl]oxy-3,5-dimethyl-6-oxooxan-2-yl]acetaldehyde
• CAS: 201054-28-6
• 化学式: C₁₅H₂₈O₄Si
• 分子量: 300.47
• InChiKey: TXCOBCWOMVHCNZ-RNJOBUHISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.16
• 重原子数：
  20
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.87
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (2S,3R,4S,5S)-3-(t-butyldimethylsilyloxy)-2,4-dimethyl-7-oxo-heptan-5-olide 在 sodium chlorite 、 2-甲基-2-丁烯 作用下， 以 水 、 叔丁醇 为溶剂， 反应 2.0h， 以99%的产率得到(2S,3R,4S,5S)-3-(t-butyldimethylsilyloxy)-2,4-dimethyl-heptan-5-olide-7-carboxylic acid
  参考文献：
  名称：

  Development of a Third-Generation Total Synthesis of (+)-Discodermolide:  An Expedient Still−Gennari-Type Fragment Coupling Utilizing an Advanced β-Ketophosphonate

  摘要：

  A novel total synthesis of the complex polyketide discodermolide, a promising anticancer agent of marine sponge origin, has been completed in 11.1% overall yield over 21 linear steps. This third-generation approach features an unprecedented Still-Gennari-type HWE olefination reaction between advanced C1-C8 beta-ketophosphonate 61 and C9-C24 aldehyde 7, introducing the (8z)alkene with 10:1 selectivity. The stereotetrad found in the C1-C8 subunit 61 was established via a highly diastereoselective boron-mediated aldol reaction/in situ reduction between ketone (S)-8 and 3-benzyloxypropanal. The (7S)-configuration was installed by the reduction of enone 73 with K-Selectride.

  DOI：

  10.1021/jo050481a
• 作为产物：
  描述：

  ethyl (E,4R,5S)-5-hydroxy-4-methyl-7-phenylmethoxyhept-2-enoate 在 palladium on activated charcoal 咪唑 、 4-二甲氨基吡啶 、 potassium tert-butylate 、 氢气 、 溶剂黄146 、 pyridinium chlorochromate 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 乙醚 、 二氯甲烷 、 水 、 N,N-二甲基甲酰胺 为溶剂， 生成 (2S,3R,4S,5S)-3-(t-butyldimethylsilyloxy)-2,4-dimethyl-7-oxo-heptan-5-olide
  参考文献：
  名称：

  (+)-Discodermolide C1-C7Segment 的立体选择性合成

  摘要：

  (+)-discodermolide 的 C1-C7 段的新的和高度立体选择性的合成描述了具有强效免疫抑制活性的海洋天然产物，其中 γ,δ-环氧丙烯酸酯与三甲基铝的立体特异性甲基化和分子内共轭加成缩醛醇盐阴离子的生成是关键步骤。

  DOI：

  10.1246/cl.1997.1191

文献信息

• Development of a Third-Generation Total Synthesis of (+)-Discodermolide:  An Expedient Still−Gennari-Type Fragment Coupling Utilizing an Advanced β-Ketophosphonate
  作者：Ian Paterson、Isabelle Lyothier

  DOI：10.1021/jo050481a

  日期：2005.7.1

  A novel total synthesis of the complex polyketide discodermolide, a promising anticancer agent of marine sponge origin, has been completed in 11.1% overall yield over 21 linear steps. This third-generation approach features an unprecedented Still-Gennari-type HWE olefination reaction between advanced C1-C8 beta-ketophosphonate 61 and C9-C24 aldehyde 7, introducing the (8z)alkene with 10:1 selectivity. The stereotetrad found in the C1-C8 subunit 61 was established via a highly diastereoselective boron-mediated aldol reaction/in situ reduction between ketone (S)-8 and 3-benzyloxypropanal. The (7S)-configuration was installed by the reduction of enone 73 with K-Selectride.
• Stereoselective Synthesis of the C₁-C₇Segment of (+)-Discodermolide
  作者：Masahiro Miyazawa、Satoshi Oonuma、Kimiyuki Maruyama、Masaaki Miyashita

  DOI：10.1246/cl.1997.1191

  日期：1997.12

  A new and highly stereoselective synthesis of the C1-C7 segment of (+)-discodermolide, the marine natural product having the potent immunosuppressive activity, is described in which the stereospecific methylation of γ,δ-epoxy acrylate with trimethylaluminum and the intramolecular conjugate addition of an acetal alkoxide anion are involved as key steps.

  (+)-discodermolide 的 C1-C7 段的新的和高度立体选择性的合成描述了具有强效免疫抑制活性的海洋天然产物，其中 γ,δ-环氧丙烯酸酯与三甲基铝的立体特异性甲基化和分子内共轭加成缩醛醇盐阴离子的生成是关键步骤。