(1S,4R,5R,7R,9R,13S,14S,15S)-3,11-dioxo-4-hydroxy-9-[(E)-2-iodoethenyl]-15-[[3-O-(2,3-di-O-methyl-α-L-fucopyranosyl)-2,4-di-O-methyl-β-D-xylo-pyranosyl]oxy]-5,8,8,14-tetramethyl-10,17,18-trioxatricyclo[11.3.1.1^4,7]octadecane | 215120-41-5

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 大环内酯类和类似物
• 英文名称: (1S,4R,5R,7R,9R,13S,14S,15S)-3,11-dioxo-4-hydroxy-9-[(E)-2-iodoethenyl]-15-[[3-O-(2,3-di-O-methyl-α-L-fucopyranosyl)-2,4-di-O-methyl-β-D-xylo-pyranosyl]oxy]-5,8,8,14-tetramethyl-10,17,18-trioxatricyclo[11.3.1.1^4,7]octadecane
• 英文别名: (1S,4R,5R,7R,9R,13S,14S,15S)-15-[[3-O-(2,3-di-O-methyl-α-L-fucopyranosyl)-2,4-di-O-methyl-β-D-xylopyranosyl]oxy]-4-hydroxy-9-[(E)-2-iodovinyl]-5,8,8,14-tetramethyl-10,17,18-trioxatricyclo[11.3.1.1^4,7]octadecane-3,11-dione；(1S,4R,5R,7R,9R,13S,14S,15S)-4-hydroxy-15-[(2S,3R,4S,5R)-4-[(2S,3S,4R,5R,6S)-5-hydroxy-3,4-dimethoxy-6-methyloxan-2-yl]oxy-3,5-dimethoxyoxan-2-yl]oxy-9-[(E)-2-iodoethenyl]-5,8,8,14-tetramethyl-10,17,18-trioxatricyclo[11.3.1.14,7]octadecane-3,11-dione
• CAS: 215120-41-5
• 化学式: C₃₆H₅₇IO₁₅
• 分子量: 856.744
• InChiKey: PRHDAGOTZDPIBX-YIMYSKAOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  52
• 可旋转键数：
  9
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.89
• 拓扑面积：
  176
• 氢给体数：
  2
• 氢受体数：
  15

反应信息

• 作为反应物：
  描述：

  tributyl(cyclohexylidenemethyl)stannane 、 (1S,4R,5R,7R,9R,13S,14S,15S)-3,11-dioxo-4-hydroxy-9-[(E)-2-iodoethenyl]-15-[[3-O-(2,3-di-O-methyl-α-L-fucopyranosyl)-2,4-di-O-methyl-β-D-xylo-pyranosyl]oxy]-5,8,8,14-tetramethyl-10,17,18-trioxatricyclo[11.3.1.1^4,7]octadecane 在 双(乙腈)氯化钯(II) 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 生成 (1S,4R,5R,7R,9R,13S,14S,15S)-9-[(E)-3-cyclohexylideneprop-1-enyl]-4-hydroxy-15-[(2S,3R,4S,5R)-4-[(2S,3S,4R,5R,6S)-5-hydroxy-3,4-dimethoxy-6-methyloxan-2-yl]oxy-3,5-dimethoxyoxan-2-yl]oxy-5,8,8,14-tetramethyl-10,17,18-trioxatricyclo[11.3.1.14,7]octadecane-3,11-dione
  参考文献：
  名称：

  Synthesis and biological evaluation of analogs of the marine toxin polycavernoside A

  摘要：

  Second generation analogs of polycavernoside A (2) possessing a side chain at C-15 different from that of the natural toxin have been synthesized. The in vivo toxicities of these new compounds (expressed as the minimal lethal dose) have been evaluated in mice (ip) and compared to 2, its aglycone (8), and polycavernoside B (9). The bioactivity profile of enynene 5 is particularly notable. (C) 1999 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0960-894x(99)00341-8
• 作为产物：
  描述：

  N-methoxy-N-methyl (2R,3S,5R)-5,7-bis[(tert-butyldimethylsilyl)oxy]-2-methyl-3-[(triisopropyl-silyl)oxy]heptamide 在 2,6-二甲基吡啶 、 9-溴-9-硼杂双环-[3.3.1]壬烷 、 chromium dichloride 、 N-溴代丁二酰亚胺(NBS) 、 18-冠醚-6 、 4 A molecular sieve 、 2,4,6-三氯苯甲酰氯 、 4-甲基苯磺酸吡啶 、 双(三甲基硅烷基)氨基钾 、 二异丁基氢化铝 、 potassium carbonate 、 戴斯-马丁氧化剂 、 氟化氢吡啶 、 臭氧 、 三乙胺 、 2,3-二氯-5,6-二氰基-1,4-苯醌 、 nickel dichloride 作用下， 以 四氢呋喃 、 吡啶 、 甲醇 、 二氯甲烷 、 水 、 N,N-二甲基甲酰胺 、 甲苯 、 乙腈 为溶剂， 反应 225.33h， 生成 (1S,4R,5R,7R,9R,13S,14S,15S)-3,11-dioxo-4-hydroxy-9-[(E)-2-iodoethenyl]-15-[[3-O-(2,3-di-O-methyl-α-L-fucopyranosyl)-2,4-di-O-methyl-β-D-xylo-pyranosyl]oxy]-5,8,8,14-tetramethyl-10,17,18-trioxatricyclo[11.3.1.1^4,7]octadecane
  参考文献：
  名称：

  通过三羟基羧酸的选择性大环内酯化来完全合成海洋毒素聚卡维诺糖苷A。

  摘要：

  DOI：

  10.1021/ja011256n

文献信息

• Stereocontrolled Elaboration of Natural (−)-Polycavernoside A, a Powerfully Toxic Metabolite of the Red Alga <i>Polycavernosa</i> <i>tsudai</i>
  作者：Leo A. Paquette、Louis Barriault、Dmitri Pissarnitski、Jeffrey N. Johnston

  DOI：10.1021/ja993487o

  日期：2000.2.1

  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.
• Polycavernoside A: The Prins Macrocyclization Approach
  作者：Sang Kook Woo、Eun Lee

  DOI：10.1021/ja1009579

  日期：2010.4.7

  An intramolecular Prins macrocyclization reaction was successfully employed in the synthesis of polycavernoside A.
• Total Synthesis and Absolute Configuration of Polycavernoside A
  作者：Kenshu Fujiwara、Akio Murai、Mari Yotsu-Yamashita、Takeshi Yasumoto

  DOI：10.1021/ja982431b

  日期：1998.10.1
• A Convergent Total Synthesis of the Macrolactone Disaccharide Toxin (−)-Polycavernoside A
  作者：Leo A. Paquette、Louis Barriault、Dmitri Pissarnitski

  DOI：10.1021/ja990384x

  日期：1999.5.1