(S)-3-Benzyloxy-2-[(1S,2R)-2-(4-methoxy-benzyloxy)-1-methyl-1-(2-triisopropylsilanyloxy-ethyl)-pent-4-enyloxy]-propan-1-ol | 874660-22-7

• 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: (S)-3-Benzyloxy-2-[(1S,2R)-2-(4-methoxy-benzyloxy)-1-methyl-1-(2-triisopropylsilanyloxy-ethyl)-pent-4-enyloxy]-propan-1-ol
• 英文别名: (2S)-2-[(3S,4R)-4-[(4-methoxyphenyl)methoxy]-3-methyl-1-tri(propan-2-yl)silyloxyhept-6-en-3-yl]oxy-3-phenylmethoxypropan-1-ol
• CAS: 874660-22-7
• 化学式: C₃₅H₅₆O₆Si
• 分子量: 600.912
• InChiKey: GRXGFGIXNDANLN-XFQWPLCWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.09
• 重原子数：
  42
• 可旋转键数：
  21
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  66.4
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  (S)-3-Benzyloxy-2-[(1S,2R)-2-(4-methoxy-benzyloxy)-1-methyl-1-(2-triisopropylsilanyloxy-ethyl)-pent-4-enyloxy]-propan-1-ol 在 碳酸氢钠 吡啶 、 2,6-二甲基吡啶 、 4-二甲氨基吡啶 、 2,2,6,6-tetramethyl-piperidine-N-oxyl 、 barium dihydroxide 、 sodium hypochlorite 、 sodium chlorite 、 Grubbs catalyst first generation 、 正丁基锂 、 2-甲基-2-丁烯 、 LiDBB 、 Crabtree catalyst 、 Stryker's reagent 、 氢气 、 碘 、 4-甲基苯磺酸吡啶 、 四丁基碘化铵 、 potassium hydride 、 二异丁基氢化铝 、 potassium carbonate 、 戴斯-马丁氧化剂 、 magnesium 、 三乙胺 、 三氟乙酸 、 potassium bromide 作用下， 以 四氢呋喃 、 甲醇 、 正己烷 、 二氯甲烷 、 水 、 N,N-二甲基甲酰胺 、 叔丁醇 、 苯 为溶剂， 反应 81.09h， 生成 2,2-Dimethyl-propionic acid (2R,3S,6R,8R)-8-[(4aR,6R,8S,8aS)-8-benzyloxy-6-(3-benzyloxy-propyl)-4,4a,6,7,8,8a-hexahydro-pyrano[3,2-b]pyran-2-ylmethyl]-6-(4-methoxy-benzyloxy)-8-methyl-3-triisopropylsilanyloxy-oxocan-2-ylmethyl ester
  参考文献：
  名称：

  Convergent, Stereoselective Synthesis of the GHIJ Fragment of Brevetoxin A

  摘要：

  A stereoselective synthesis of the GHIJ fragment of brevetoxin A utilizing a convergent assembly strategy is described. Glycolate alkylation, ring-closing metathesis, and Hosomi-Sakurai reactions were central operations in the construction of the G ring and J ring subunits, which were united through a Horner-Wadsworth-Emmons coupling. Subsequent dehydrative cyclization produced an endocyclic enol ether that was further elaborated to the tetracyclic GHIJ fragment of brevetoxin A.

  DOI：

  10.1021/ol0526625
• 作为产物：
  描述：

  苄基碘甲基醚 在 锂硼氢 、 sodium bis(trimethylsilyl)amide 作用下， 以 四氢呋喃 、 甲醇 、 甲苯 为溶剂， 反应 1.25h， 生成 (S)-3-Benzyloxy-2-[(1S,2R)-2-(4-methoxy-benzyloxy)-1-methyl-1-(2-triisopropylsilanyloxy-ethyl)-pent-4-enyloxy]-propan-1-ol
  参考文献：
  名称：

  Convergent, Stereoselective Synthesis of the GHIJ Fragment of Brevetoxin A

  摘要：

  A stereoselective synthesis of the GHIJ fragment of brevetoxin A utilizing a convergent assembly strategy is described. Glycolate alkylation, ring-closing metathesis, and Hosomi-Sakurai reactions were central operations in the construction of the G ring and J ring subunits, which were united through a Horner-Wadsworth-Emmons coupling. Subsequent dehydrative cyclization produced an endocyclic enol ether that was further elaborated to the tetracyclic GHIJ fragment of brevetoxin A.

  DOI：

  10.1021/ol0526625

文献信息

• Enantioselective Total Synthesis of Brevetoxin A: Unified Strategy for the B, E, G, and J Subunits
  作者：Michael T. Crimmins、J. Michael Ellis、Kyle A. Emmitte、Pamela A. Haile、Patrick J. McDougall、Jonathan D. Parrish、J. Lucas Zuccarello

  DOI：10.1002/chem.200900776

  日期：2009.9.14

  oxacycles, as well as 22 tetrahedral stereocenters. Herein, we describe a unified approach to the B, E, G, and J rings based upon a ring‐closing metathesis strategy from the corresponding dienes. The enolate technologies developed in our laboratory allowed access to the precursor acyclic dienes for the B, E, and G medium‐ring ethers. The strategies developed for the syntheses of these four monocycles

  Brevetoxin A 是一种十环梯形毒素，具有 5、6、7、8 和 9 元氧杂环，以及 22 个四面体立体中心。在此，我们描述了基于来自相应二烯的闭环复分解策略的 B、E、G 和 J 环的统一方法。我们实验室开发的烯醇技术允许获得 B、E 和 G 中环醚的前体无环二烯。为合成这四个单环而开发的策略最终提供了数克数量的每个环，支持我们为完成短毒素 A 的收敛合成所做的努力。
• Convergent, Stereoselective Synthesis of the GHIJ Fragment of Brevetoxin A
  作者：Michael T. Crimmins、J. Lucas Zuccarello、Pamela A. Cleary、Jonathan D. Parrish

  DOI：10.1021/ol0526625

  日期：2006.1.1

  A stereoselective synthesis of the GHIJ fragment of brevetoxin A utilizing a convergent assembly strategy is described. Glycolate alkylation, ring-closing metathesis, and Hosomi-Sakurai reactions were central operations in the construction of the G ring and J ring subunits, which were united through a Horner-Wadsworth-Emmons coupling. Subsequent dehydrative cyclization produced an endocyclic enol ether that was further elaborated to the tetracyclic GHIJ fragment of brevetoxin A.