(4E,11E,13E)-(1S,6R,10R,15S,18R,19R,20S)-18-((S)-3-iodo-1-methylbut-3-enyl)-8,8,15-trimethyl-19-triethylsilanyloxy-7,9,17,23-tetraoxatricyclo[18.2.1.06,10]tricosa-4,11,13-trien-16-one | 945265-81-6

• 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: (4E,11E,13E)-(1S,6R,10R,15S,18R,19R,20S)-18-((S)-3-iodo-1-methylbut-3-enyl)-8,8,15-trimethyl-19-triethylsilanyloxy-7,9,17,23-tetraoxatricyclo[18.2.1.06,10]tricosa-4,11,13-trien-16-one
• 英文别名: (4E,11E,13E)-(1S,6R,10R,15S,18R,19R,20S)-18-((S)-3-iodo-1-methylbut-3-enyl)-8,8,15-trimethyl-19-triethylsilanyloxy-7,9,17,23-tetraoxatricyclo[18.2.1.0^6,10]tricosa-4,11,13-trien-16-one
• CAS: 945265-81-6
• 化学式: C₃₃H₅₃IO₆Si
• 分子量: 700.77
• InChiKey: HBLYKDKEXVQAAX-VPTOWSRASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.43
• 重原子数：
  41.0
• 可旋转键数：
  8.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  63.22
• 氢给体数：
  0.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  (4E,11E,13E)-(1S,6R,10R,15S,18R,19R,20S)-18-((S)-3-iodo-1-methylbut-3-enyl)-8,8,15-trimethyl-19-triethylsilanyloxy-7,9,17,23-tetraoxatricyclo[18.2.1.06,10]tricosa-4,11,13-trien-16-one 、 Tributyl-((E)-4-methyl-penta-1,4-dienyl)-stannane 在 四(三苯基膦)钯 溶剂黄146 、 copper(l) chloride 作用下， 以 四氢呋喃 、 水 为溶剂， 以32%的产率得到2-epi-19-epi-amphidinolide E
  参考文献：
  名称：

  Total synthesis of amphidinolide E and amphidinolide E stereoisomers

  摘要：

  Four amphidinolide E stereoisomers, amphidinolide E (1), 2-epi-amphidinolide E (2), 19-epi-amphidinolide E (3), and 2-epi-19-epi- amphidinolide E (4), have been synthesized via the judicious union of aldehyde 5, allylsilanes 7 or 8, acids 9 or 10, and vinylstannane 6. The C19 stereocenters of the C19 epimeric allylsilanes 7 and 8 were introduced via crotylboration reactions early in the synthesis. [3+2] Annulation reactions of aldehyde 5 with allylsilanes 7 and 8 were employed to set the core tetrahydrofuran units of 1-4. Finally, the C2 stereo-center was installed by esterification using acid 9, without incident, or with acid 10, in which case an unexpected and completely stereoselective inversion of C2 occurs. (C) 2007 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2007.02.058
• 作为产物：
  描述：

  (S)-2,2-diethyl-4-[(1R,2S)-1-(4-methoxybenzyloxy)-2-methylpent-4-ynyl]-[1,3]dioxolane 在 Grubbs catalyst first generation 咪唑 、 sodium periodate 、 Bu3SnAlEt2 、 4 A molecular sieve 、 三氟化硼乙醚 、 四丁基氟化铵 、 溶剂黄146 、 三乙胺 、 2,3-二氯-5,6-二氰基-1,4-苯醌 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 、 水 、 N,N-二甲基甲酰胺 、 甲苯 为溶剂， 反应 3.0h， 生成 (4E,11E,13E)-(1S,6R,10R,15S,18R,19R,20S)-18-((S)-3-iodo-1-methylbut-3-enyl)-8,8,15-trimethyl-19-triethylsilanyloxy-7,9,17,23-tetraoxatricyclo[18.2.1.06,10]tricosa-4,11,13-trien-16-one
  参考文献：
  名称：

  Total synthesis of amphidinolide E and amphidinolide E stereoisomers

  摘要：

  Four amphidinolide E stereoisomers, amphidinolide E (1), 2-epi-amphidinolide E (2), 19-epi-amphidinolide E (3), and 2-epi-19-epi- amphidinolide E (4), have been synthesized via the judicious union of aldehyde 5, allylsilanes 7 or 8, acids 9 or 10, and vinylstannane 6. The C19 stereocenters of the C19 epimeric allylsilanes 7 and 8 were introduced via crotylboration reactions early in the synthesis. [3+2] Annulation reactions of aldehyde 5 with allylsilanes 7 and 8 were employed to set the core tetrahydrofuran units of 1-4. Finally, the C2 stereo-center was installed by esterification using acid 9, without incident, or with acid 10, in which case an unexpected and completely stereoselective inversion of C2 occurs. (C) 2007 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2007.02.058