tert-butyl (3R,4S,4aR,5S)-3-((benzyloxy)methyl)-4-(2,3-bis(tert-butoxycarbonyl)guanidino)-1-((tert-butoxycarbonyl)imino)-4a,5-dihydroxyhexahydropyrrolo[1,2-c]pyrimidine-2(1H)-carboxylate | 1185281-39-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯
• 英文名称: tert-butyl (3R,4S,4aR,5S)-3-((benzyloxy)methyl)-4-(2,3-bis(tert-butoxycarbonyl)guanidino)-1-((tert-butoxycarbonyl)imino)-4a,5-dihydroxyhexahydropyrrolo[1,2-c]pyrimidine-2(1H)-carboxylate
• CAS: 1185281-39-3
• 化学式: C₃₆H₅₆N₆O₁₁
• 分子量: 748.874
• InChiKey: ZVTVVTGZDAQXQI-BPMMCVLLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.64
• 重原子数：
  53.0
• 可旋转键数：
  5.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  210.15
• 氢给体数：
  4.0
• 氢受体数：
  11.0

反应信息

• 作为反应物：
  描述：

  tert-butyl (3R,4S,4aR,5S)-3-((benzyloxy)methyl)-4-(2,3-bis(tert-butoxycarbonyl)guanidino)-1-((tert-butoxycarbonyl)imino)-4a,5-dihydroxyhexahydropyrrolo[1,2-c]pyrimidine-2(1H)-carboxylate 在 Pearlman's catalist 、 氢气 作用下， 以82%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
• 作为产物：
  描述：

  、 N,N'-bis-Boc-S-methyl-isothiourea 在 三乙胺 、 mercury dichloride 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 1.0h， 以106 mg的产率得到tert-butyl (3R,4S,4aR,5S)-3-((benzyloxy)methyl)-4-(2,3-bis(tert-butoxycarbonyl)guanidino)-1-((tert-butoxycarbonyl)imino)-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