(4E,11E,13E)-(1S,6R,10R,15R,18R,19R,20S)-8,8,15-trimethyl-18-((S)-1-methylbut-3-ynyl)-19-triethylsilanyloxy-7,9,17,23-tetraoxatricyclo[18.2.1.06,10]tricosa-4,11,13-trien-16-one | 945265-91-8

• 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,15R,18R,19R,20S)-8,8,15-trimethyl-18-((S)-1-methylbut-3-ynyl)-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,15R,18R,19R,20S)-8,8,15-trimethyl-18-((S)-1-methylbut-3-ynyl)-19-triethylsilanyloxy-7,9,17,23-tetraoxatricyclo[18.2.1.0^6,10]tricosa-4,11,13-trien-16-one
• CAS: 945265-91-8
• 化学式: C₃₃H₅₂O₆Si
• 分子量: 572.858
• InChiKey: ZDCGZUAACZHIHQ-ADXUYFIBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.11
• 重原子数：
  40.0
• 可旋转键数：
  7.0
• 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,15R,18R,19R,20S)-8,8,15-trimethyl-18-((S)-1-methylbut-3-ynyl)-19-triethylsilanyloxy-7,9,17,23-tetraoxatricyclo[18.2.1.06,10]tricosa-4,11,13-trien-16-one 在 Bu3SnAlEt2 、 N-碘代丁二酰亚胺 作用下， 以 四氢呋喃 、 正己烷 、 甲苯 、 二氯甲烷 为溶剂， 以34 mg的产率得到(4E,11E,13E)-(1S,6R,10R,15R,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
• 作为产物：
  描述：

  (3S,4R)-4-((S)-2,2-diethyl-[1,3]dioxolan-4-yl)-4-(4-methoxybenzyloxy)-3-methylbutan-1-ol 在 Grubbs catalyst first generation 咪唑 、 sodium periodate 、 正丁基锂 、 pyridine-SO3 complex 、 4 A molecular sieve 、 三氟化硼乙醚 、 四丁基氟化铵 、 溶剂黄146 、 二甲基亚砜 、 三乙胺 、 N,N-二异丙基乙胺 、 三苯基膦 、 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,15R,18R,19R,20S)-8,8,15-trimethyl-18-((S)-1-methylbut-3-ynyl)-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