(2R,4R,5S)-4-hydroxy-2-methyl-5-(3-methylbut-3-enyl)-2-propyltetrahydrofuran | 944942-93-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (2R,4R,5S)-4-hydroxy-2-methyl-5-(3-methylbut-3-enyl)-2-propyltetrahydrofuran
• 英文别名: (2R,4R,5S)-4-hydroxy-2-methyl-5-(3-methyl-3-butenyl)-2-propyloxolane；(2S,3R,5R)-5-methyl-2-(3-methylbut-3-enyl)-5-propyloxolan-3-ol
• CAS: 944942-93-2
• 化学式: C₁₃H₂₄O₂
• 分子量: 212.332
• InChiKey: FUVNYZATLDGNRH-FRRDWIJNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  15
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.85
• 拓扑面积：
  29.5
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (2R,4R,5S)-4-hydroxy-2-methyl-5-(3-methylbut-3-enyl)-2-propyltetrahydrofuran 在 RuCl2(1,3-dimesityl-imidazolidin-2-yl)(PCy3)(=CHPh) 4-二甲氨基吡啶 、 2,4,6-三氯苯甲酰氯 、 碳酸氢钠 、 戴斯-马丁氧化剂 、 三乙胺 、 三氟乙酸 作用下， 以 四氢呋喃 、 二氯甲烷 、 水 、 甲苯 为溶剂， 反应 81.0h， 生成 (2S,3R,5R)-5-methyl-2-(3-methylbut-3-enyl)-5-propyltetrahydrofuran-3-yl (2E,11E)-(4S,7R,9S,10R)-7,9-dihydroxy-4,7,10-trimethyl-6-oxo-12-phenyldodeca-2,11-dienoate
  参考文献：
  名称：

  Total Synthesis of Amphidinolide Y by Formation of Trisubstituted (E)-Double Bond via Ring-Closing Metathesis of Densely Functionalized Alkenes

  摘要：

  Amphidinolide Y, a 17-membered cytotoxic macrolide isolated from marine dinoflagellates, has been synthesized via ring-closing metathesis to assemble the congested trisubstituted (E)-double bond. The seco precursor was prepared from readily available chiral synthons with the tetrahydrofuran ring formed via 5-endo epoxide ring-opening cyclization. It was found that the C6-keto seco substrate showed higher reactivity toward Grubbs' second generation catalyst while Schrock's Mo catalyst was completely inactive for formation of the macrocycle.

  DOI：

  10.1021/ol0710360
• 作为产物：
  描述：

  C₂₀H₂₉NO₃ 在 lithium aluminium tetrahydride 作用下， 以 乙醚 为溶剂， 以89%的产率得到(2R,4R,5S)-4-hydroxy-2-methyl-5-(3-methylbut-3-enyl)-2-propyltetrahydrofuran
  参考文献：
  名称：

  Jung, Jae Hoon; Lee, Eun, Angewandte Chemie - International Edition, 2009, vol. 48, p. 5698 - 5700

  摘要：

  DOI：

文献信息

• Stereocontrolled Total Synthesis of Amphidinolide X via a Silicon-Tethered Metathesis Reaction
  作者：Carles Rodríguez-Escrich、Fèlix Urpí、Jaume Vilarrasa

  DOI：10.1021/ol8021676

  日期：2008.11.20

  Two esterifications and an RCM to create the challenging trisubstituted C12-C13 double bond were required in the total synthesis of amphidinolide X (1) reported here. Assembling the three fragments in this order, no RCM occurred or the process yielded mainly isomer Z. However, generating the E double bond first, by a new variant of a Si-tethered metathesis (using Schrock's catalyst), and carrying out

  在这里报告的两性霉素X（1）的总合成中，需要两次酯化反应和一个RCM来形成具有挑战性的三取代C12-C13双键。按此顺序组装三个片段，没有发生RCM或该过程主要产生异构体Z。但是，首先通过Si系留复分解的新变体（使用Schrock催化剂）生成E双键，然后进行酯化和宏观内酯化步骤之后，仅获得1。
• Total Synthesis of Amphidinolide X and Its 12<i>Z</i>-Isomer by Formation of the C12-C13 Trisubstituted Double Bond via Ring-Closing Metathesis
  作者：Wei-Min Dai、Jinlong Wu、Yile Chen、Jian Jin、Jianshu Lou、Qiaojun He

  DOI：10.1055/s-2008-1077885

  日期：——

  Amphidinolide X, a 16-membered cytotoxic macro­diolide, and its 12Z-isomer have been synthesized via ring-closing metathesis (RCM) for assembling the C12-C13 trisubstituted double bond. A 29:71 E/Z mixture was obtained from the seco substrate appended with a bulky C8-ODPS group in 50-65% combined yields by using 20 mol% of the second-generation Grubbs initiator and the corresponding indenylidene ruthenium complex. Amphidinolide X and 12Z-isomer exhibit similar cytotoxicity (IC50: 7.6-13.9 µg/mL) against A549, KB, and HL60 cell lines.

  一种 16 元细胞毒性大环内酯 Amphidinolide X 及其 12Z 异构体是通过环闭合偏析 (RCM) 合成的，以组装 C12-C13 三取代双键。通过使用 20 摩尔百分率的第二代格拉布斯引发剂和相应的亚茚基钌络合物，从附加了一个笨重的 C8-ODPS 基团的仲底物中获得了 29:71 的 E/Z 混合物，总产率为 50-65%。蚜虫内酯 X 和 12Z 异构体对 A549、KB 和 HL60 细胞株具有相似的细胞毒性（IC50：7.6-13.9 µg/mL）。
• Synthesis of amphidinolide Y precursors
  作者：Laura Mola、Anna Olivella、Fèlix Urpí、Jaume Vilarrasa

  DOI：10.1016/j.tetlet.2013.12.047

  日期：2014.1

  The Negishi coupling between a chiral C3 synthon and an iodoalkene arising from 3-butyn-l-ol, which gave the C3-C9 fragment of amphidinolide Y, was the starting point of a formal total synthesis of this marine natural product. By means of Sharpless ADH and TADDOL-mediated crotylation, the full western fragment (C1-C11) was obtained, which was coupled with the eastern fragment (3-hydroxyoxolane derivative). The penultimate step (ring-closing metathesis, with G-II, H-G-II, or Nitro-Grela reagents, under several conditions) posed great difficulties. The cyclization was achieved with 15c (7,9-bis-O-TES) and 15d (7-O-TES, 9-O-TBS); more than stoichiometric amounts of the H-G-II Ru complex were required for complete conversion. (C) 2013 Elsevier Ltd. All rights reserved.