Methyl (2E,4E,10E)-(S)-(+)-11-(tert-butoxycarbonyl)-7-methylundeca-2,4,10-trienoate | 168131-80-4

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: Methyl (2E,4E,10E)-(S)-(+)-11-(tert-butoxycarbonyl)-7-methylundeca-2,4,10-trienoate
• 英文别名: 12-O-tert-butyl 1-O-methyl (2E,4E,7S,10E)-7,11-dimethyldodeca-2,4,10-trienedioate
• CAS: 168131-80-4
• 化学式: C₁₉H₃₀O₄
• 分子量: 322.445
• InChiKey: FJMBAJRLSHQFGI-FAYPQYCFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.8
• 重原子数：
  23
• 可旋转键数：
  11
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.58
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  Methyl (2E,4E,10E)-(S)-(+)-11-(tert-butoxycarbonyl)-7-methylundeca-2,4,10-trienoate 在 sodium hydroxide 、 二异丁基氢化铝 、 三乙胺 作用下， 以 四氢呋喃 、 乙醇 、 甲苯 为溶剂， 反应 8.0h， 生成
  参考文献：
  名称：

  A Short Synthesis of Natural (-)-Oblongolide via an Intramolecular or a Transannular Diels-Alder Reaction

  摘要：

  The absolute configuration of naturally occurring oblongolide is confirmed as (3aS,5aR,7S,9aS, 9bS)-3a,5a,6,7,8,9,9a,9b-octahydro-7,9b-dimethylnaphtho[1,2-c]furan-1(3H)-one (1) on the basis of a six-stage or an eight-stage synthesis from (-)-citronellol involving a steric-controlled, regioselective reduction and an intramolecular Diels-Alder (IMDA) reaction or a transannular Diels-Alder (TDA) reaction as the key steps. (-)-Citronellol (5) was converted into methyl (2E,4E,10E)-(S)-(+)-11-(tert-butoxycarbonyl)-7-methylundeca-2,4,10-trienoate (7) by sequential Lemiuex-Johnson oxidation, Wittig olefination, pyridinium dichromate oxidation, and Wadsworth-Emmons-Horner alkenation. A regioselective reduction of the methoxycarbonyl group in 7 afforded tert-butyl (2E,8E,10E)-(S)-(+)-2,6-dimethyl-12-hydroxydodeca-2,8,10-trienoate (8) from which oblongolide (1) was obtained via an IMDA reaction. The macrocyclic (2E,8E,10E)-(S)-(+)-2,6-dimethyldodeca-2,8,10-trieno-1,12-lactone derived from 8 underwent a highly stereoselective TDA reaction to give 1 at a lower reaction temperature, in a shorter reaction time and in a better yield than the analogous IMDA reaction.

  DOI：

  10.1021/jo00123a011
• 作为产物：
  描述：

  (叔丁氧基羰基亚甲基)三苯基磷烷 在 sodium hydroxide 、 重铬酸吡啶 、 3 A molecular sieve 、 sodium hexamethyldisilazane 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 5.08h， 生成 Methyl (2E,4E,10E)-(S)-(+)-11-(tert-butoxycarbonyl)-7-methylundeca-2,4,10-trienoate
  参考文献：
  名称：

  A Short Synthesis of Natural (-)-Oblongolide via an Intramolecular or a Transannular Diels-Alder Reaction

  摘要：

  The absolute configuration of naturally occurring oblongolide is confirmed as (3aS,5aR,7S,9aS, 9bS)-3a,5a,6,7,8,9,9a,9b-octahydro-7,9b-dimethylnaphtho[1,2-c]furan-1(3H)-one (1) on the basis of a six-stage or an eight-stage synthesis from (-)-citronellol involving a steric-controlled, regioselective reduction and an intramolecular Diels-Alder (IMDA) reaction or a transannular Diels-Alder (TDA) reaction as the key steps. (-)-Citronellol (5) was converted into methyl (2E,4E,10E)-(S)-(+)-11-(tert-butoxycarbonyl)-7-methylundeca-2,4,10-trienoate (7) by sequential Lemiuex-Johnson oxidation, Wittig olefination, pyridinium dichromate oxidation, and Wadsworth-Emmons-Horner alkenation. A regioselective reduction of the methoxycarbonyl group in 7 afforded tert-butyl (2E,8E,10E)-(S)-(+)-2,6-dimethyl-12-hydroxydodeca-2,8,10-trienoate (8) from which oblongolide (1) was obtained via an IMDA reaction. The macrocyclic (2E,8E,10E)-(S)-(+)-2,6-dimethyldodeca-2,8,10-trieno-1,12-lactone derived from 8 underwent a highly stereoselective TDA reaction to give 1 at a lower reaction temperature, in a shorter reaction time and in a better yield than the analogous IMDA reaction.

  DOI：

  10.1021/jo00123a011

文献信息

• A Short Synthesis of Natural (-)-Oblongolide via an Intramolecular or a Transannular Diels-Alder Reaction
  作者：Tony K. M. Shing、Jun Yang

  DOI：10.1021/jo00123a011

  日期：1995.9

  The absolute configuration of naturally occurring oblongolide is confirmed as (3aS,5aR,7S,9aS, 9bS)-3a,5a,6,7,8,9,9a,9b-octahydro-7,9b-dimethylnaphtho[1,2-c]furan-1(3H)-one (1) on the basis of a six-stage or an eight-stage synthesis from (-)-citronellol involving a steric-controlled, regioselective reduction and an intramolecular Diels-Alder (IMDA) reaction or a transannular Diels-Alder (TDA) reaction as the key steps. (-)-Citronellol (5) was converted into methyl (2E,4E,10E)-(S)-(+)-11-(tert-butoxycarbonyl)-7-methylundeca-2,4,10-trienoate (7) by sequential Lemiuex-Johnson oxidation, Wittig olefination, pyridinium dichromate oxidation, and Wadsworth-Emmons-Horner alkenation. A regioselective reduction of the methoxycarbonyl group in 7 afforded tert-butyl (2E,8E,10E)-(S)-(+)-2,6-dimethyl-12-hydroxydodeca-2,8,10-trienoate (8) from which oblongolide (1) was obtained via an IMDA reaction. The macrocyclic (2E,8E,10E)-(S)-(+)-2,6-dimethyldodeca-2,8,10-trieno-1,12-lactone derived from 8 underwent a highly stereoselective TDA reaction to give 1 at a lower reaction temperature, in a shorter reaction time and in a better yield than the analogous IMDA reaction.