O-((S)-2-((S)-1-(((S)-2-(((3S,4R,5S)-4-(((benzyloxy)carbonyl)amino)-5-methyl-3-((triisopropylsilyl)oxy)heptanoyl)oxy)-3-methylbutanoyl)-L-leucyl)-N-methylpyrrolidine-2-carboxamido)-3-(4-methoxyphenyl)propanoyl)-N-(tert-butoxycarbonyl)-L-threonine | 345664-75-7

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: O-((S)-2-((S)-1-(((S)-2-(((3S,4R,5S)-4-(((benzyloxy)carbonyl)amino)-5-methyl-3-((triisopropylsilyl)oxy)heptanoyl)oxy)-3-methylbutanoyl)-L-leucyl)-N-methylpyrrolidine-2-carboxamido)-3-(4-methoxyphenyl)propanoyl)-N-(tert-butoxycarbonyl)-L-threonine
• CAS: 345664-75-7
• 化学式: C₆₁H₉₇N₅O₁₅Si
• 分子量: 1168.55
• InChiKey: SAPKSRMLELSQLH-PIVWDLEZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.36
• 重原子数：
  82.0
• 可旋转键数：
  30.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  254.74
• 氢给体数：
  4.0
• 氢受体数：
  14.0

反应信息

• 作为反应物：
  描述：

  O-((S)-2-((S)-1-(((S)-2-(((3S,4R,5S)-4-(((benzyloxy)carbonyl)amino)-5-methyl-3-((triisopropylsilyl)oxy)heptanoyl)oxy)-3-methylbutanoyl)-L-leucyl)-N-methylpyrrolidine-2-carboxamido)-3-(4-methoxyphenyl)propanoyl)-N-(tert-butoxycarbonyl)-L-threonine 在 palladium on activated charcoal N-甲基吗啉 、 盐酸 、 氢气 、 (benzotriazo-1-yloxy)tris(dimethylamino)phosphonium hexafluorophosphate 、 N,N-二异丙基乙胺 、 N-[(dimethylamino)-3-oxo-1H-1,2,3-triazolo[4,5-b]pyridin-1-yl-methylene]-N-methylmethanaminium hexafluorophosphate 作用下， 以 甲醇 、 二氯甲烷 、 乙酸乙酯 、 N,N-二甲基甲酰胺 为溶剂， -30.0~20.0 ℃ 、393.01 kPa 条件下， 反应 9.0h， 生成 N-prolyl [Hiv²]didemnin A
  参考文献：
  名称：

  Total Syntheses and Biological Investigations of Tamandarins A and B and Tamandarin A Analogs

  摘要：

  Tamandarins A (1) and B (2), two natural products similar in structure to didemnin B (3), were recently isolated from a Brazilian marine ascidian of the family Didemnidae. The cytotoxicity of 1 was reported to be somewhat more potent in vitro than that of 3 against various human cancer cell lines. The present account describes the first total syntheses of 1 and 2, and the syntheses of tamandarin A side chain analogues. The cytotoxicity data for these compounds show that the side chain modifications exhibit a parallel effect for both didemnins and tamandarins. This observation supports tamandarins' role as didemnins' mimic.

  DOI：

  10.1021/ja010222c
• 作为产物：
  描述：

  (2R,3S)-2-Benzyloxycarbonylamino-3-methyl-pentanoic acid pentafluorophenyl ester 在 吗啉 、 2,6-二甲基吡啶 、 4-二甲氨基吡啶 、 sodium hydroxide 、 四(三苯基膦)钯 、 钾硼氢 、 N,N-二异丙基乙胺 、 N,N'-二环己基碳二亚胺 、 bromo-tris(1-pyrrolidinyl)phosphonium hexafluorophosphate 、 magnesium bromide 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 为溶剂， 生成 O-((S)-2-((S)-1-(((S)-2-(((3S,4R,5S)-4-(((benzyloxy)carbonyl)amino)-5-methyl-3-((triisopropylsilyl)oxy)heptanoyl)oxy)-3-methylbutanoyl)-L-leucyl)-N-methylpyrrolidine-2-carboxamido)-3-(4-methoxyphenyl)propanoyl)-N-(tert-butoxycarbonyl)-L-threonine
  参考文献：
  名称：

  Total Syntheses and Biological Investigations of Tamandarins A and B and Tamandarin A Analogs

  摘要：

  Tamandarins A (1) and B (2), two natural products similar in structure to didemnin B (3), were recently isolated from a Brazilian marine ascidian of the family Didemnidae. The cytotoxicity of 1 was reported to be somewhat more potent in vitro than that of 3 against various human cancer cell lines. The present account describes the first total syntheses of 1 and 2, and the syntheses of tamandarin A side chain analogues. The cytotoxicity data for these compounds show that the side chain modifications exhibit a parallel effect for both didemnins and tamandarins. This observation supports tamandarins' role as didemnins' mimic.

  DOI：

  10.1021/ja010222c

文献信息

• The First Total Synthesis of (−)-Tamandarin A
  作者：Bo Liang、Padma Portonovo、Matthew D. Vera、Dong Xiao、Madeleine M. Joullié

  DOI：10.1021/ol9910058

  日期：1999.10.1

  [GRAPHICS]Tamandarin A (1), a newly isolated natural product similar in structure to didemnin a (2), was shown to be somewhat more active in vitro than 2 against pancreatic carcinoma with an ED50 value 1.5 to 2 ng/mL. We report here the first total synthesis of 1. The key steps include a practical stereoselective synthesis of the Hiv-isostatine unit, high-yielding linear precursor formation, a successful macrocyclization, and coupling of the macrocycle with the side chain to afford tamandarin A (1).