phenyl 2,4-di-O-acetyl-1-thio-β-D-xylopyranoside | 170451-36-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: phenyl 2,4-di-O-acetyl-1-thio-β-D-xylopyranoside
• 英文别名: [(3R,4S,5R,6S)-5-acetyloxy-4-hydroxy-6-phenylsulfanyloxan-3-yl] acetate
• CAS: 170451-36-2
• 化学式: C₁₅H₁₈O₆S
• 分子量: 326.37
• InChiKey: BTRJSIYVFHZRHR-BARDWOONSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  22
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  107
• 氢给体数：
  1
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  phenyl 2,4-di-O-acetyl-1-thio-β-D-xylopyranoside 在 氢氧化钾 、 silver perchlorate 、 tin(ll) chloride 作用下， 以 甲醇 、 乙醚 为溶剂， 反应 1.0h， 生成
  参考文献：
  名称：

  Stereocontrolled Elaboration of Natural (−)-Polycavernoside A, a Powerfully Toxic Metabolite of the Red Alga Polycavernosa tsudai

  摘要：

  A stereoselective total synthesis of natural levorotatory polycavemoside A (1) has been achieved. initial investigations produced the properly activated disaccharide unit 18b via the conjoining of building blocks originating from L-fucose and D-xylose. This objective was followed by preparation of the phenylsulfonyl-substituted tetrahydropyran 23 and aldehyde 30. After proper linking of these key compounds, important information had to be garnered on the sequence of steps that would ultimately result in successful access to 1. Although oxidation to generate alpha-diketone 35 and unmasking of the C-13 hydroxyl did give rise efficiently to lactol 36, this functionality did not pave the way for ensuring macrolactonization. When this sequence of steps was reversed, it was indeed possible to arrive at the heavily functionalized precursor 43. However, numerous experiments failed to result in the requisite activation of C-16 for attachment of the trienyl side chain. However, if the E-vinyl iodide was elaborated in advance of alpha-diketone generation, glycosidation, and complete side chain construction, arrival at 1 proceeded without unsurmountable complications to furnish the targeted marine toxin.

  DOI：

  10.1021/ja993487o
• 作为产物：
  描述：

  D-吡喃木糖 在 吡啶 、 三氟化硼乙醚 、 四氯化锡 作用下， 以 苯 为溶剂， 反应 0.33h， 生成 phenyl 2,4-di-O-acetyl-1-thio-β-D-xylopyranoside
  参考文献：
  名称：

  Stereocontrolled Elaboration of Natural (−)-Polycavernoside A, a Powerfully Toxic Metabolite of the Red Alga Polycavernosa tsudai

  摘要：

  A stereoselective total synthesis of natural levorotatory polycavemoside A (1) has been achieved. initial investigations produced the properly activated disaccharide unit 18b via the conjoining of building blocks originating from L-fucose and D-xylose. This objective was followed by preparation of the phenylsulfonyl-substituted tetrahydropyran 23 and aldehyde 30. After proper linking of these key compounds, important information had to be garnered on the sequence of steps that would ultimately result in successful access to 1. Although oxidation to generate alpha-diketone 35 and unmasking of the C-13 hydroxyl did give rise efficiently to lactol 36, this functionality did not pave the way for ensuring macrolactonization. When this sequence of steps was reversed, it was indeed possible to arrive at the heavily functionalized precursor 43. However, numerous experiments failed to result in the requisite activation of C-16 for attachment of the trienyl side chain. However, if the E-vinyl iodide was elaborated in advance of alpha-diketone generation, glycosidation, and complete side chain construction, arrival at 1 proceeded without unsurmountable complications to furnish the targeted marine toxin.

  DOI：

  10.1021/ja993487o

文献信息

• Studies directed toward the total synthesis of polycavernoside A. Enantioselective synthesis of the disaccharide component
  作者：Jeffrey N. Johnston、Leo A. Paquette

  DOI：10.1016/0040-4039(95)00789-f

  日期：1995.6

  Adaptation of the Mukaiyama-Nicolaou protocol to the coupling of a monounprotected thioglycoside to a glycosyl fluoride is capable of delivering the unusual disaccharide present in the title toxin.

  Mukaiyama-Nicolaou规程适应单未保护的硫代糖苷与糖基氟化物的偶联能够递送标题毒素中存在的异常二糖。
• Total Synthesis of Polycavernoside A, A Lethal Toxin of the Red Alga <i>Polycavernosa </i><i>t</i><i>sudai</i>
  作者：Paul R. Blakemore、Cindy C. Browder、Jian Hong、Christopher M. Lincoln、Pavel A. Nagornyy、Lonnie A. Robarge、Duncan J. Wardrop、James D. White

  DOI：10.1021/jo0503862

  日期：2005.7.1

  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%.