(1R,5S,7S,10S,12S,13S,15S)-13-(tert-butyldimethylsilyloxy)-7-(2-((R,Z)-3-methoxy-2-methylbut-1-enyl)oxazol-4-yl)-10,12-dimethyl-9,17-dioxo-8,19-dioxabicyclo[13.3.1]nonadecan-5-yl acetate | 1236147-14-0

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 大环内酯类和类似物
• 英文名称: (1R,5S,7S,10S,12S,13S,15S)-13-(tert-butyldimethylsilyloxy)-7-(2-((R,Z)-3-methoxy-2-methylbut-1-enyl)oxazol-4-yl)-10,12-dimethyl-9,17-dioxo-8,19-dioxabicyclo[13.3.1]nonadecan-5-yl acetate
• CAS: 1236147-14-0
• 化学式: C₃₆H₅₉NO₉Si
• 分子量: 677.951
• InChiKey: DDGVGUWFXJPVPJ-WQLSDRQQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.76
• 重原子数：
  47.0
• 可旋转键数：
  7.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  123.39
• 氢给体数：
  0.0
• 氢受体数：
  10.0

反应信息

• 作为反应物：
  描述：

  三甲基氯硅烷 、 (1R,5S,7S,10S,12S,13S,15S)-13-(tert-butyldimethylsilyloxy)-7-(2-((R,Z)-3-methoxy-2-methylbut-1-enyl)oxazol-4-yl)-10,12-dimethyl-9,17-dioxo-8,19-dioxabicyclo[13.3.1]nonadecan-5-yl acetate 在 四氯化钛 、 1,2-二溴乙烷 、 锌 、 二溴甲烷 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 以78%的产率得到(1R,5S,7S,10S,12S,13S,15S)-13-(tert-butyldimethylsilyloxy)-7-(2-((R,Z)-3-methoxy-2-methylbut-1-enyl)oxazol-4-yl)-10,12-dimethyl-17-methylene-9-dioxo-8,19-dioxabicyclo[13.3.1]nonadecan-5-yl acetate
  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：

  (1R,5S,7S,10S,12S,13S,15S)-13-(tert-butyldimethylsilyloxy)-17,17-dimethoxy-7-(2-((R,Z)-3-methoxy-2-methylbut-1-enyl)oxazol-4-yl)-10,12-dimethyl-9-oxo-8,19-dioxabicyclo[13.3.1]nonadecan-5-yl acetate 在 camphorsulfonic acid 作用下， 以 二氯甲烷 、 丙酮 为溶剂， 反应 4.0h， 以91%的产率得到(1R,5S,7S,10S,12S,13S,15S)-13-(tert-butyldimethylsilyloxy)-7-(2-((R,Z)-3-methoxy-2-methylbut-1-enyl)oxazol-4-yl)-10,12-dimethyl-9,17-dioxo-8,19-dioxabicyclo[13.3.1]nonadecan-5-yl acetate
  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