(2S,3R,5R)-5-methyl-2-(3-methylbut-3-enyl)-5-propyltetrahydrofuran-3-yl (2E)-(4S,7R,9S,10R)-9-(tert-butyldimethylsilyloxy)-4,7,10-trimethyl-6-oxo-7-(triethylsilyl)oxydodeca-2,11-dienoate | 944943-01-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (2S,3R,5R)-5-methyl-2-(3-methylbut-3-enyl)-5-propyltetrahydrofuran-3-yl (2E)-(4S,7R,9S,10R)-9-(tert-butyldimethylsilyloxy)-4,7,10-trimethyl-6-oxo-7-(triethylsilyl)oxydodeca-2,11-dienoate
• 英文别名: [(2S,3R,5R)-5-methyl-2-(3-methylbut-3-enyl)-5-propyloxolan-3-yl] (2E,4S,7R,9S,10R)-9-[tert-butyl(dimethyl)silyl]oxy-4,7,10-trimethyl-6-oxo-7-triethylsilyloxydodeca-2,11-dienoate
• CAS: 944943-01-5
• 化学式: C₄₀H₇₄O₆Si₂
• 分子量: 707.195
• InChiKey: RVVUYHQVOVYQEJ-NLJOZZMWSA-N

物化性质

• 沸点：
  659.3±55.0 °C(predicted)
• 密度：
  0.95±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  11.14
• 重原子数：
  48
• 可旋转键数：
  24
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  71.1
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  (2S,3R,5R)-5-methyl-2-(3-methylbut-3-enyl)-5-propyltetrahydrofuran-3-yl (2E)-(4S,7R,9S,10R)-9-(tert-butyldimethylsilyloxy)-4,7,10-trimethyl-6-oxo-7-(triethylsilyl)oxydodeca-2,11-dienoate 在 2,6-二甲基吡啶 、 氟化氢吡啶 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 2.0h， 生成
  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：

  3-甲基-3-丁烯-1-醇 在 2,6-二甲基吡啶 、 4-二甲氨基吡啶 、 ammonium cerium(IV) nitrate 、 偶氮二甲酸二异丙酯 、 AD-mix-β 、 2,4,6-三氯苯甲酰氯 、 乙基溴化镁 、 potassium trimethylsilonate 、 双(三甲基硅烷基)氨基钾 、 二异丁基氢化铝 、 碳酸氢钠 、 戴斯-马丁氧化剂 、 三乙胺 、 三苯基膦 、 三氟乙酸 、 2,3-二氯-5,6-二氰基-1,4-苯醌 作用下， 以 四氢呋喃 、 乙醚 、 正己烷 、 二氯甲烷 、 水 、 甲苯 、 乙腈 、 叔丁醇 为溶剂， 反应 115.5h， 生成 (2S,3R,5R)-5-methyl-2-(3-methylbut-3-enyl)-5-propyltetrahydrofuran-3-yl (2E)-(4S,7R,9S,10R)-9-(tert-butyldimethylsilyloxy)-4,7,10-trimethyl-6-oxo-7-(triethylsilyl)oxydodeca-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

文献信息

• 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.