(2S,3R,4R,5S)-3-Benzyloxy-6-fluoro-4,5-dimethoxy-2-methyl-tetrahydro-pyran | 861120-58-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (2S,3R,4R,5S)-3-Benzyloxy-6-fluoro-4,5-dimethoxy-2-methyl-tetrahydro-pyran
• CAS: 861120-58-3
• 化学式: C₁₅H₂₁FO₄
• 分子量: 284.328
• InChiKey: DBLWMMXMZXPNNP-SBYDSHQYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.32
• 重原子数：
  20.0
• 可旋转键数：
  5.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  36.92
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  (2S,3R,4R,5S)-3-Benzyloxy-6-fluoro-4,5-dimethoxy-2-methyl-tetrahydro-pyran 在 氢氧化钾 、 silver perchlorate 、 tin(ll) chloride 作用下， 以 甲醇 、 乙醚 为溶剂， 生成 (2S,3R,4S,5R)-4-((2S,3S,4R,5R,6S)-5-Benzyloxy-3,4-dimethoxy-6-methyl-tetrahydro-pyran-2-yloxy)-2-phenylsulfanyl-tetrahydro-pyran-3,5-diol
  参考文献：
  名称：

  Total Synthesis of Polycavernoside A, A Lethal Toxin of the Red Alga Polycavernosa tsudai

  摘要：

  Two approaches to the synthesis of the aglycon 120 of polycavernoside A (1) were developed, only one of which was completed. The successful "second-generation" route assembled the aglycon seco acids 102 and 106 via Nozaki-Hiyama-Kishi coupling of aldehyde 70, prepared from methyl (S)3-hydroxy-2-methylpropionate (72) and (S)-pantolactone (73), with vinyl bromide 71. The latter was obtained from a sequence which commenced from the silyl ether 24 of 3-hydroxypropionaldehyde and entailed cyclization of (Z)-zeta -hydroxy-alpha,beta-unsaturated ester 82. Regioselective Yamaguchi lactonization of trihydroxycarboxylic acids 102 and 106 and subsequent functional-group adjustments led to macrolactone 120, to which the fucopyranosylxylopyranoside moiety was attached. Stille coupling of the glycosidated aglycon 128 with dienylstannane 129 furnished polycavernoside A in a synthesis for which the longest linear sequence was 25 steps. The overall yield to lactone 120 was 4.7%.

  DOI：

  10.1021/jo0503862
• 作为产物：
  描述：

  (2S,3R,4R,5S,6R)-3-Benzyloxy-4,5-dimethoxy-2-methyl-6-phenylsulfanyl-tetrahydro-pyran 在 N-溴代丁二酰亚胺(NBS) 作用下， 以 二氯甲烷 为溶剂， 以81%的产率得到(2S,3R,4R,5S)-3-Benzyloxy-6-fluoro-4,5-dimethoxy-2-methyl-tetrahydro-pyran
  参考文献：
  名称：

  Total Synthesis of Polycavernoside A, A Lethal Toxin of the Red Alga Polycavernosa tsudai

  摘要：

  Two approaches to the synthesis of the aglycon 120 of polycavernoside A (1) were developed, only one of which was completed. The successful "second-generation" route assembled the aglycon seco acids 102 and 106 via Nozaki-Hiyama-Kishi coupling of aldehyde 70, prepared from methyl (S)3-hydroxy-2-methylpropionate (72) and (S)-pantolactone (73), with vinyl bromide 71. The latter was obtained from a sequence which commenced from the silyl ether 24 of 3-hydroxypropionaldehyde and entailed cyclization of (Z)-zeta -hydroxy-alpha,beta-unsaturated ester 82. Regioselective Yamaguchi lactonization of trihydroxycarboxylic acids 102 and 106 and subsequent functional-group adjustments led to macrolactone 120, to which the fucopyranosylxylopyranoside moiety was attached. Stille coupling of the glycosidated aglycon 128 with dienylstannane 129 furnished polycavernoside A in a synthesis for which the longest linear sequence was 25 steps. The overall yield to lactone 120 was 4.7%.

  DOI：

  10.1021/jo0503862

文献信息

• Relative Configuration of a Marine Toxin Polycavernoside-A
  作者：Kenshu Fujiwara、Seiji Amano、Akio Murai

  DOI：10.1246/cl.1995.855

  日期：1995.9

  Combination of the sugar and tetrahydropyran parts of polycavernoside-A, which has been isolated as one of toxic principles from the red alga Polycavernosa tsudai, revealed the whole relative configuration of the compound from the spectral data.

  从红藻 Polycavernosa tsudai 中分离出的毒性成分之一的多腔苷-A 的糖部分和四氢吡喃部分的组合，揭示了该化合物的整体相对构型，基于光谱数据。