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 | 1185281-47-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯并嘧啶类
• 英文名称: 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
• CAS: 1185281-47-3
• 化学式: C₃₇H₅₈N₆O₁₂
• 分子量: 778.901
• InChiKey: YXMGRFDGAMOXOV-LGARNSPHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.1
• 重原子数：
  55
• 可旋转键数：
  16
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.68
• 拓扑面积：
  219
• 氢给体数：
  4
• 氢受体数：
  13

反应信息

• 作为反应物：
  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
• 作为产物：
  描述：

  tert-butyl (3R,4S,4aR,5S)-4-amino-1-((tert-butoxycarbonyl)imino)-4a,5-dihydroxy-3-(((4-methoxybenzyl)oxy)methyl)hexahydropyrrolo[1,2-c]pyrimidine-2(1H)-carboxylate 、 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2.75 g的产率得到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
  参考文献：
  名称：

  （+）-氨基甲酰基糖原毒素和（+）-Gonyautoxin 3的全合成

  摘要：

  通过使用依赖于邻近基团参与的新颖的，构象控制的胍环化过程，可以轻松构建复杂的毒素（STX）骨架。通过在天然和非天然STX衍生物的合成中使用该方法，证实了该方法的实用性。

  DOI：

  10.1021/ol1006696

文献信息

• Total Synthesis of (−)- and (+)-Decarbamoyloxysaxitoxin and (+)-Saxitoxin
  作者：Osamu Iwamoto、Ryoko Shinohara、Kazuo Nagasawa

  DOI：10.1002/asia.200800382

  日期：2009.2.2

  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.
• Total Synthesis of (+)-Decarbamoylsaxitoxin and (+)-Gonyautoxin 3
  作者：Osamu Iwamoto、Kazuo Nagasawa

  DOI：10.1021/ol1006696

  日期：2010.5.7

  Facile construction of the complex saxitoxin (STX) skeleton is carried out by using a novel, conformationally controlled, guanidine cyclization process that relies on the use of neighboring group participation. The utility of this methodology is verified by its employment in syntheses of both natural and unnatural STX derivatives.

  通过使用依赖于邻近基团参与的新颖的，构象控制的胍环化过程，可以轻松构建复杂的毒素（STX）骨架。通过在天然和非天然STX衍生物的合成中使用该方法，证实了该方法的实用性。