苯丙腈,b-氟-a-羟基- | 143084-69-9

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 蛤蚌毒素、膝沟藻毒素及其衍生物
• 中文名称: 苯丙腈,b-氟-a-羟基-
• 中文别名: (3aS-(3aalpha,4alpha,10aR*))-2,6-二氨基-3a,4,8,9-四氢-4-甲基-1H,10H-吡咯并(1,2-c)嘌呤-10,10-二醇
• 英文名称: (+)-decarbamoyloxysaxitoxin
• 英文别名: (+)-doSTX；Decarbamoyloxysaxitoxin；(3aS,4S,10aS)-2,6-diamino-4-methyl-3a,4,8,9-tetrahydro-1H-pyrrolo[1,2-c]purine-10,10-diol
• CAS: 143084-69-9
• 化学式: C₉H₁₆N₆O₂
• 分子量: 240.265
• InChiKey: ICEQSJLPASDDEC-PJPYAQQDSA-N

物化性质

• 沸点：
  529.5±60.0 °C(Predicted)
• 密度：
  2.09±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  -3.6
• 重原子数：
  17
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  133
• 氢给体数：
  5
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  在 三氟乙酸吡啶 、 二甲基亚砜 、 N,N'-二异丙基碳二亚胺 作用下， 生成 苯丙腈,b-氟-a-羟基-
  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

文献信息

• Synthesis and Identification of decarbamoyloxySaxitoxins in Toxic Microalgae and their Reactions with the Oxygenase, SxtT, Reveal Saxitoxin Biosynthesis
  作者：Mayu Hakamada、Chihiro Tokairin、Hayate Ishizuka、Kanna Adachi、Toma Osawa、Shiori Aonuma、Ryosuke Hirozumi、Shigeki Tsuchiya、Yuko Cho、Yuta Kudo、Keiichi Konoki、Yasukatsu Oshima、Kazuo Nagasawa、Mari Yotsu‐Yamashita

  DOI：10.1002/chem.202304238

  日期：2024.3.25

  dd-doSTX (2), 12β-deoxy-doSTX (3), 12α-deoxy-doSTX (4) and doSTX (5) were synthesized, and 2, 3, and 5 were identified in the toxin-producing marine dinoflagellates and a freshwater cyanobacterium. In addition, conversion of 2 to 3, and 4 to 5 by SxtT with VanB was confirmed. These results support that 2 is a biosynthetic precursor of STX (1), and that ring and side-chain hydroxylation proceed after

  合成了去氨甲酰氧基石房蛤毒素 (doSTXs)、dd-doSTX ( 2 )、12β-deoxy-doSTX ( 3 )、12α-deoxy-doSTX ( 4 ) 和doSTX ( 5 )，并在毒素中鉴定出了2、3和5 个毒素。产生海洋甲藻和淡水蓝藻。另外，确认了通过SxtT与VanB将2转化为3、4转化为5 。这些结果支持2是STX( 1 )的生物合成前体，并且在STX生物合成中环化和侧链羟基化在环化之后进行。