ethyl 2-<1(S)-hydroxy-2(R)-(methylthio)-2-<((4R,5S)-4-methyl-5-phenyl-2-oxazolidinyl)carbonyl>ethyl>-6-amino-5-methylpyrimidine-4-carboxylate | 157968-10-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二嗪类
• 英文名称: ethyl 2-<1(S)-hydroxy-2(R)-(methylthio)-2-<((4R,5S)-4-methyl-5-phenyl-2-oxazolidinyl)carbonyl>ethyl>-6-amino-5-methylpyrimidine-4-carboxylate
• CAS: 157968-10-0
• 化学式: C₂₂H₂₆N₄O₆S
• 分子量: 474.538
• InChiKey: LUHZZPALQPKIBC-BASLNEPJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.42
• 重原子数：
  33.0
• 可旋转键数：
  7.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.41
• 拓扑面积：
  144.94
• 氢给体数：
  2.0
• 氢受体数：
  10.0

反应信息

• 作为反应物：
  描述：

  ethyl 2-<1(S)-hydroxy-2(R)-(methylthio)-2-<((4R,5S)-4-methyl-5-phenyl-2-oxazolidinyl)carbonyl>ethyl>-6-amino-5-methylpyrimidine-4-carboxylate 在 palladium on activated charcoal 乙醇 、 三(2-氯乙基)胺 、 氨 、 氢气 、 三正丁基氢锡 、 三苯基膦 、 偶氮二甲酸二乙酯 作用下， 以 四氢呋喃 、 甲醇 、 苯 为溶剂， 反应 39.5h， 生成 3-(6-amino-4-(ethoxycarbonyl)-5-methylpyrimidin-2-yl)-3(S)-aminopropionamide
  参考文献：
  名称：

  Total Synthesis of Bleomycin A2 and Related Agents. 2. Synthesis of (-)-Pyrimidoblamic Acid, epi-(+)-Pyrimidoblamic Acid, (+)-Desacetamidopyrimidoblamic Acid, and (-)-Descarboxamidopyrimidoblamic Acid

  摘要：

  Full details of concise syntheses of (-)-pyrimidoblamic acid (1), the authentic heterocyclic core of the bleomycin A(2) metal binding domain, as well as the key substructure analogs epi-(+)-pyrimidoblamic acid (2), (+)-desacetamidopyrimidoblamic acid (3), and (-)-descarboxamidppyrimidoblamic acid (4) are described. Key to the approach is the implementation of an inverse electron demand [4 + 2] cycloaddition reaction of 2,4,6-tris(ethoxycarbonyl)-1,3,5-triazine with 1-(dibenzylamino)-1-propyne or in situ generated 1,1-diaminopropene for the one-step preparation of an appropriately functionalized pyrimidine nucleus. The development and subsequent implementation of a diastereoselective imine addition reaction of optically active N-acyloxazolidinone enolates provided a stereocontrolled introduction of the pyrimidoblamic acid C2 acetamido side chain. Chemical studies which unambiguously establish and confirm the absolute configuration of the C2 acetamido side chain are detailed, and their extension to the synthesis of (-)-descarboxamidopyrimidoblamic acid (4) is described.

  DOI：

  10.1021/ja00092a012
• 作为产物：
  描述：

  ethyl 4-amino-2-(hydroxymethyl)-5-methylpyrimidine-6-carboxylate 在 manganese(IV) oxide 、 三氟甲磺酸二丁硼 、 N,N-二异丙基乙胺 作用下， 以 乙腈 为溶剂， 反应 7.0h， 生成 ethyl 2-<1(S)-hydroxy-2(R)-(methylthio)-2-<((4R,5S)-4-methyl-5-phenyl-2-oxazolidinyl)carbonyl>ethyl>-6-amino-5-methylpyrimidine-4-carboxylate
  参考文献：
  名称：

  Total Synthesis of Bleomycin A2 and Related Agents. 2. Synthesis of (-)-Pyrimidoblamic Acid, epi-(+)-Pyrimidoblamic Acid, (+)-Desacetamidopyrimidoblamic Acid, and (-)-Descarboxamidopyrimidoblamic Acid

  摘要：

  Full details of concise syntheses of (-)-pyrimidoblamic acid (1), the authentic heterocyclic core of the bleomycin A(2) metal binding domain, as well as the key substructure analogs epi-(+)-pyrimidoblamic acid (2), (+)-desacetamidopyrimidoblamic acid (3), and (-)-descarboxamidppyrimidoblamic acid (4) are described. Key to the approach is the implementation of an inverse electron demand [4 + 2] cycloaddition reaction of 2,4,6-tris(ethoxycarbonyl)-1,3,5-triazine with 1-(dibenzylamino)-1-propyne or in situ generated 1,1-diaminopropene for the one-step preparation of an appropriately functionalized pyrimidine nucleus. The development and subsequent implementation of a diastereoselective imine addition reaction of optically active N-acyloxazolidinone enolates provided a stereocontrolled introduction of the pyrimidoblamic acid C2 acetamido side chain. Chemical studies which unambiguously establish and confirm the absolute configuration of the C2 acetamido side chain are detailed, and their extension to the synthesis of (-)-descarboxamidopyrimidoblamic acid (4) is described.

  DOI：

  10.1021/ja00092a012