(2S,3R,4S,6R)-6-allyl-4-(benzyloxy)-6-iodomethyltetrahydro-3-methyl-2H-pyran | 223693-12-7

• 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,4S,6R)-6-allyl-4-(benzyloxy)-6-iodomethyltetrahydro-3-methyl-2H-pyran
• 英文别名: (2S,3R,4S,6S)-6-(iodomethyl)-3-methyl-4-phenylmethoxy-2-prop-2-enyloxane
• CAS: 223693-12-7
• 化学式: C₁₇H₂₃IO₂
• 分子量: 386.273
• InChiKey: RBIHFQVMQIVFER-HJWJTTGWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.8
• 重原子数：
  20
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (2S,3R,4S,6R)-6-allyl-4-(benzyloxy)-6-iodomethyltetrahydro-3-methyl-2H-pyran 在 4-二甲氨基吡啶 、 sodium chlorite 、 sodium periodate 、 sodium dihydrogenphosphate 、 四氧化锇 、 正丁基锂 、 N-甲基吲哚酮 、 2-甲基-2-丁烯 、 potassium tert-butylate 、 水 、 戴斯-马丁氧化剂 、 对甲苯磺酸 、 三乙胺 、 2,3-二氯-5,6-二氰基-1,4-苯醌 作用下， 以 四氢呋喃 、 甲醇 、 正己烷 、 二氯甲烷 、 水 、 甲苯 、 叔丁醇 为溶剂， 反应 22.92h， 生成 (1S,4R,5R.7R,9S,13S,14R,15S)-15-(benzyloxy)-9-[(tert-butyldiphenylsiloxy)methyl]-4-hydroxy-5,8,8,14-tetramethyl-10,17,18-trioxatricyclo[11.3.1.14,7]octadecane-3,11-dione
  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：

  (3R,4S,6S)-2-Allyl-6-(tert-butyl-diphenyl-silanyloxymethyl)-3-methyl-tetrahydro-pyran-2,4-diol 在 咪唑 、 三乙基硅烷 、 四丁基氟化铵 、 碘 、 四氯化锡 、 sodium hydride 、 三苯基膦 、 sodium iodide 作用下， 以 四氢呋喃 、 二氯甲烷 、 苯 为溶剂， 反应 4.66h， 生成 (2S,3R,4S,6R)-6-allyl-4-(benzyloxy)-6-iodomethyltetrahydro-3-methyl-2H-pyran
  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

• 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