(2S,4S,5S)-methyl 5-(tert-butyldimethylsilyloxy)-6-((2S,6S)-6-formyl-4,4-dimethoxytetrahydro-2H-pyran-2-yl)-2,4-dimethylhexanoate | 1236147-08-2

• 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: (2S,4S,5S)-methyl 5-(tert-butyldimethylsilyloxy)-6-((2S,6S)-6-formyl-4,4-dimethoxytetrahydro-2H-pyran-2-yl)-2,4-dimethylhexanoate
• 英文别名: methyl (2S,4S,5S)-5-[tert-butyl(dimethyl)silyl]oxy-6-[(2S,6S)-6-formyl-4,4-dimethoxyoxan-2-yl]-2,4-dimethylhexanoate
• CAS: 1236147-08-2
• 化学式: C₂₃H₄₄O₇Si
• 分子量: 460.684
• InChiKey: DSYAJYXEMYWITH-HVTWWXFQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.34
• 重原子数：
  31
• 可旋转键数：
  13
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.91
• 拓扑面积：
  80.3
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  (2S,4S,5S)-methyl 5-(tert-butyldimethylsilyloxy)-6-((2S,6S)-6-formyl-4,4-dimethoxytetrahydro-2H-pyran-2-yl)-2,4-dimethylhexanoate 、 (2-((4R,6S)-6-(2-((R,Z)-3-methoxy-2-methylbut-1-enyl)oxazol-4-yl)-2,2-dimethyl-1,3-dioxan-4-yl)ethyl)triphenylphosphonium iodide 在 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 以71%的产率得到(2S,4S,5S)-methyl 5-(tert-butyldimethylsilyloxy)-6-((2S,6S)-4,4-dimethoxy-6-((Z)-3-((4S,6S)-6-(2-((R,Z)-3-methoxy-2-methylbut-1-enyl)oxazol-4-yl)-2,2-dimethyl-1,3-dioxan-4-yl)prop-1-enyl)tetrahydro-2H-pyran-2-yl)-2,4-dimethylhexanoate
  参考文献：
  名称：

  Total Synthesis of Enigmazole A from Cinachyrella enigmatica. Bidirectional Bond Constructions with an Ambident 2,4-Disubstituted Oxazole Synthon

  摘要：

  The first total synthesis of the cytotoxic marine macrolide enigmazole A has been completed in 22 steps (longest linear sequence). The sensitive, densely functionalized 2,4-disubstituted oxazole fragment was constructed using an efficient Negishi-type coupling of an oxazol-2-ylzinc reagent formed directly from the parent ethyl 2-iodooxazole-4-carboxylate by zinc insertion. Other key steps include a hetero-Diels-Alder cycloaddition to form the central embedded pyran ring, a Wittig reaction to unite Eastern and Western hemispheres, and a ring size-selective Keck macrolactonization.

  DOI：

  10.1021/ja1016975
• 作为产物：
  描述：

  (2S,4S,5S)-methyl 5-(tert-butyldimethylsilyloxy)-6-((2S,6S)-6-(hydroxymethyl)-4,4-dimethoxytetrahydro-2H-pyran-2-yl)-2,4-dimethylhexanoate 在 草酰氯 、 二甲基亚砜 、 N,N-二异丙基乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 0.5h， 生成 (2S,4S,5S)-methyl 5-(tert-butyldimethylsilyloxy)-6-((2S,6S)-6-formyl-4,4-dimethoxytetrahydro-2H-pyran-2-yl)-2,4-dimethylhexanoate
  参考文献：
  名称：

  Total Synthesis of Enigmazole A from Cinachyrella enigmatica. Bidirectional Bond Constructions with an Ambident 2,4-Disubstituted Oxazole Synthon

  摘要：

  The first total synthesis of the cytotoxic marine macrolide enigmazole A has been completed in 22 steps (longest linear sequence). The sensitive, densely functionalized 2,4-disubstituted oxazole fragment was constructed using an efficient Negishi-type coupling of an oxazol-2-ylzinc reagent formed directly from the parent ethyl 2-iodooxazole-4-carboxylate by zinc insertion. Other key steps include a hetero-Diels-Alder cycloaddition to form the central embedded pyran ring, a Wittig reaction to unite Eastern and Western hemispheres, and a ring size-selective Keck macrolactonization.

  DOI：

  10.1021/ja1016975