tert-butyl (3R,4S,4aR,5S)-4-(2,3-bis(tert-butoxycarbonyl)guanidino)-1-((tert-butoxycarbonyl)imino)-4a,5-dihydroxy-3-(hydroxymethyl)hexahydropyrrolo[1,2-c]pyrimidine-2(1H)-carboxylate | 1185281-43-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二嗪烷类
• 英文名称: tert-butyl (3R,4S,4aR,5S)-4-(2,3-bis(tert-butoxycarbonyl)guanidino)-1-((tert-butoxycarbonyl)imino)-4a,5-dihydroxy-3-(hydroxymethyl)hexahydropyrrolo[1,2-c]pyrimidine-2(1H)-carboxylate
• CAS: 1185281-43-9
• 化学式: C₂₉H₅₀N₆O₁₁
• 分子量: 658.75
• InChiKey: MVEAKNDGRQWUGR-KKDNJGSRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.42
• 重原子数：
  46.0
• 可旋转键数：
  2.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.79
• 拓扑面积：
  221.15
• 氢给体数：
  5.0
• 氢受体数：
  11.0

反应信息

• 作为反应物：
  描述：

  tert-butyl (3R,4S,4aR,5S)-4-(2,3-bis(tert-butoxycarbonyl)guanidino)-1-((tert-butoxycarbonyl)imino)-4a,5-dihydroxy-3-(hydroxymethyl)hexahydropyrrolo[1,2-c]pyrimidine-2(1H)-carboxylate 、 三氯乙酰异氰酸酯 在 potassium carbonate 作用下， 以 二氯甲烷 、 甲醇 为溶剂， 反应 25.0h， 以35%的产率得到tert-butyl (3R,4S,4aR,5S)-4-(2,3-bis(tert-butoxycarbonyl)guanidino)-1-((tert-butoxycarbonyl)imino)-3-((carbamoyloxy)methyl)-4a,5-dihydroxyhexahydropyrrolo[1,2-c]pyrimidine-2(1H)-carboxylate
  参考文献：
  名称：

  Total Synthesis of (−)- and (+)-Decarbamoyloxysaxitoxin and (+)-Saxitoxin

  摘要：

  AbstractPlaying the sax: The enantioselective total syntheses of (−)‐ and (+)‐decarbamoyloxysaxitoxin (doSTX) and (+)‐saxitoxin (STX) are reported. A new methodology was developed for the synthesis of STXs, featuring discriminative reduction of the nitro group and NO bond in nitroisoxazolidine.magnified imageEnantioselective total syntheses of (−)‐ and (+)‐decarbamoyloxysaxitoxin (doSTX) and (+)‐saxitoxin (STX) were achieved. The characteristic spiro‐fused cyclic guanidine structure of STX was constructed by oxidation at the C4 position with IBX via an α‐iminium carbonyl intermediate and acid‐promoted cyclization of guanidine at the C5 position. A second‐generation methodology was developed for the synthesis of STX, featuring discriminative reduction of the nitro group and NO bond in nitroisoxazolidine. This approach provides efficient access to the key diamine intermediate for STXs.

  DOI：

  10.1002/asia.200800382
• 作为产物：
  描述：

  tert-butyl (3R,4S,4aR,5S)-4-[bis[(2-methylpropan-2-yl)oxycarbonylamino]methylideneamino]-4a,5-dihydroxy-3-[(4-methoxyphenyl)methoxymethyl]-1-[(2-methylpropan-2-yl)oxycarbonylimino]-4,5,6,7-tetrahydro-3H-pyrrolo[1,2-c]pyrimidine-2-carboxylate 在 水 、 2,3-二氯-5,6-二氰基-1,4-苯醌 作用下， 以 二氯甲烷 为溶剂， 反应 1.0h， 以90%的产率得到tert-butyl (3R,4S,4aR,5S)-4-(2,3-bis(tert-butoxycarbonyl)guanidino)-1-((tert-butoxycarbonyl)imino)-4a,5-dihydroxy-3-(hydroxymethyl)hexahydropyrrolo[1,2-c]pyrimidine-2(1H)-carboxylate
  参考文献：
  名称：

  Total Synthesis of (−)- and (+)-Decarbamoyloxysaxitoxin and (+)-Saxitoxin

  摘要：

  AbstractPlaying the sax: The enantioselective total syntheses of (−)‐ and (+)‐decarbamoyloxysaxitoxin (doSTX) and (+)‐saxitoxin (STX) are reported. A new methodology was developed for the synthesis of STXs, featuring discriminative reduction of the nitro group and NO bond in nitroisoxazolidine.magnified imageEnantioselective total syntheses of (−)‐ and (+)‐decarbamoyloxysaxitoxin (doSTX) and (+)‐saxitoxin (STX) were achieved. The characteristic spiro‐fused cyclic guanidine structure of STX was constructed by oxidation at the C4 position with IBX via an α‐iminium carbonyl intermediate and acid‐promoted cyclization of guanidine at the C5 position. A second‐generation methodology was developed for the synthesis of STX, featuring discriminative reduction of the nitro group and NO bond in nitroisoxazolidine. This approach provides efficient access to the key diamine intermediate for STXs.

  DOI：

  10.1002/asia.200800382