(2S,4S,5S)-methyl 5-(tert-butyldimethylsilyloxy)-2,4-dimethyl-6-(4-oxo-6-(pent-4-enyl)-tetrahydro-2H-pyran-2-yl)hexanoate | 1236147-25-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (2S,4S,5S)-methyl 5-(tert-butyldimethylsilyloxy)-2,4-dimethyl-6-(4-oxo-6-(pent-4-enyl)-tetrahydro-2H-pyran-2-yl)hexanoate
• CAS: 1236147-25-3
• 化学式: C₂₅H₄₆O₅Si
• 分子量: 454.723
• InChiKey: CYUHPWCOCXKMDY-WCKIQHKBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.08
• 重原子数：
  31.0
• 可旋转键数：
  12.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.84
• 拓扑面积：
  61.83
• 氢给体数：
  0.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  (2S,4S,5S)-methyl 5-(tert-butyldimethylsilyloxy)-2,4-dimethyl-6-(4-oxo-6-(pent-4-enyl)-tetrahydro-2H-pyran-2-yl)hexanoate 在 lithium tri-t-butoxyaluminum hydride 作用下， 以 四氢呋喃 为溶剂， 反应 2.5h， 以65%的产率得到(2S,4S,5S)-methyl 5-(tert-butyldimethylsilyloxy)-6-((2R,4S,6R)-4-hydroxy-6-(pent-4-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-(4,4-dimethoxy-6-(pent-4-enyl)-tetrahydro-2H-pyran-2-yl)-2,4-dimethylhexanoate 在 对甲苯磺酸 作用下， 以 二氯甲烷 、 水 为溶剂， 反应 0.67h， 以88%的产率得到(2S,4S,5S)-methyl 5-(tert-butyldimethylsilyloxy)-2,4-dimethyl-6-(4-oxo-6-(pent-4-enyl)-tetrahydro-2H-pyran-2-yl)hexanoate
  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