ethyl (2E,4S,6S,7S,8Z,10E,12E)-9-bromo-14-hydroxy-7-(methoxymethoxy)-2,4,6,12-tetramethyltetradeca-2,8,10,12-tetraenoate | 198289-51-9

• 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: ethyl (2E,4S,6S,7S,8Z,10E,12E)-9-bromo-14-hydroxy-7-(methoxymethoxy)-2,4,6,12-tetramethyltetradeca-2,8,10,12-tetraenoate
• CAS: 198289-51-9
• 化学式: C₂₂H₃₅BrO₅
• 分子量: 459.421
• InChiKey: FQWIRHJPRWNHJG-HLIZLOKWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.9
• 重原子数：
  28
• 可旋转键数：
  14
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.59
• 拓扑面积：
  65
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  ethyl (2E,4S,6S,7S,8Z,10E,12E)-9-bromo-14-hydroxy-7-(methoxymethoxy)-2,4,6,12-tetramethyltetradeca-2,8,10,12-tetraenoate 在 咪唑 、 sodium amalgam 、 N-甲基吲哚酮 、 四丙基高钌酸铵 、 2,6-二叔丁基-4-甲基苯酚 、 二异丁基氢化铝 、 牛血清白蛋白 作用下， 以 甲醇 、 二氯甲烷 、 N,N-二甲基甲酰胺 、 甲苯 为溶剂， 反应 13.67h， 生成 (1S,2S,4aS,5S,6S,8S,8aR)-2-[(E)-4-[tert-butyl(dimethyl)silyl]oxybut-2-en-2-yl]-5-(methoxymethoxy)-1,6,8-trimethyl-4a,5,6,7,8,8a-hexahydro-2H-naphthalene-1-carbaldehyde
  参考文献：
  名称：

  A Formal Total Synthesis of (+)-Tetronolide, the Aglycon of the Tetrocarcins:  Enantio- and Diastereoselective Syntheses of the Octahydronaphthalene (Bottom-Half) and Spirotetronate (Top-Half) Fragments

  摘要：

  A formal total synthesis of (+)-tetronolide, the aglycon of the tetrocarcins, has been achieved by virtue of the development of highly diastereo-and enantioselective syntheses of the bottom- and top-half fragments 4 and 5 reported herein. These fragments previously served as key intermediates in Yoshii's pioneering total synthesis of (+)-tetronolide, The synthesis of the bottom-half octahydronaphthalene unit 4 features the intramolecular Diels-Alder reaction of tetraenal 20 and proceeds in 17 steps and 5-6% yield from D-glyceraldehyde pentylidene acetal 8. The synthesis of the spirotetronate fragment 5 features the highly enantioselective exo selective Diels-Alder reaction of triene 37 and chiral dienophile 25b and proceeds in 14 steps and 10% overall yield from cis-2-butene-1,4-diol (38). An enantioselective synthesis of Boeckman's top-half cyclohexene fragment 6 sia the exo selective Diels-Alder reaction of diene 24 and dienophile 25a was also developed, but this route was deemed too inefficient for use in a projected total synthesis of the natural product. The syntheses of 5 and 6 provide important information on the utility of chiral dienophiles 25a and 25b in organic synthesis.

  DOI：

  10.1021/jo970960c
• 作为产物：
  描述：

  (S)-3-[(2S,4S,5S)-5-((R)-2,2-Diethyl-[1,3]dioxolan-4-yl)-5-methoxymethoxy-2,4-dimethyl-pentanoyl]-4-isopropyl-oxazolidin-2-one 在 四(三苯基膦)钯 、 甲酸 、 potassium metaperiodate 、 二异丁基氢化铝 、 potassium hydrogencarbonate 、 三苯基膦 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 水 、 甲苯 为溶剂， 反应 36.17h， 生成 ethyl (2E,4S,6S,7S,8Z,10E,12E)-9-bromo-14-hydroxy-7-(methoxymethoxy)-2,4,6,12-tetramethyltetradeca-2,8,10,12-tetraenoate
  参考文献：
  名称：

  A Formal Total Synthesis of (+)-Tetronolide, the Aglycon of the Tetrocarcins:  Enantio- and Diastereoselective Syntheses of the Octahydronaphthalene (Bottom-Half) and Spirotetronate (Top-Half) Fragments

  摘要：

  A formal total synthesis of (+)-tetronolide, the aglycon of the tetrocarcins, has been achieved by virtue of the development of highly diastereo-and enantioselective syntheses of the bottom- and top-half fragments 4 and 5 reported herein. These fragments previously served as key intermediates in Yoshii's pioneering total synthesis of (+)-tetronolide, The synthesis of the bottom-half octahydronaphthalene unit 4 features the intramolecular Diels-Alder reaction of tetraenal 20 and proceeds in 17 steps and 5-6% yield from D-glyceraldehyde pentylidene acetal 8. The synthesis of the spirotetronate fragment 5 features the highly enantioselective exo selective Diels-Alder reaction of triene 37 and chiral dienophile 25b and proceeds in 14 steps and 10% overall yield from cis-2-butene-1,4-diol (38). An enantioselective synthesis of Boeckman's top-half cyclohexene fragment 6 sia the exo selective Diels-Alder reaction of diene 24 and dienophile 25a was also developed, but this route was deemed too inefficient for use in a projected total synthesis of the natural product. The syntheses of 5 and 6 provide important information on the utility of chiral dienophiles 25a and 25b in organic synthesis.

  DOI：

  10.1021/jo970960c

文献信息

• A Formal Total Synthesis of (+)-Tetronolide, the Aglycon of the Tetrocarcins:  Enantio- and Diastereoselective Syntheses of the Octahydronaphthalene (Bottom-Half) and Spirotetronate (Top-Half) Fragments
  作者：William R. Roush、Melissa L. Reilly、Kazuo Koyama、Bradley B. Brown

  DOI：10.1021/jo970960c

  日期：1997.12.1

  A formal total synthesis of (+)-tetronolide, the aglycon of the tetrocarcins, has been achieved by virtue of the development of highly diastereo-and enantioselective syntheses of the bottom- and top-half fragments 4 and 5 reported herein. These fragments previously served as key intermediates in Yoshii's pioneering total synthesis of (+)-tetronolide, The synthesis of the bottom-half octahydronaphthalene unit 4 features the intramolecular Diels-Alder reaction of tetraenal 20 and proceeds in 17 steps and 5-6% yield from D-glyceraldehyde pentylidene acetal 8. The synthesis of the spirotetronate fragment 5 features the highly enantioselective exo selective Diels-Alder reaction of triene 37 and chiral dienophile 25b and proceeds in 14 steps and 10% overall yield from cis-2-butene-1,4-diol (38). An enantioselective synthesis of Boeckman's top-half cyclohexene fragment 6 sia the exo selective Diels-Alder reaction of diene 24 and dienophile 25a was also developed, but this route was deemed too inefficient for use in a projected total synthesis of the natural product. The syntheses of 5 and 6 provide important information on the utility of chiral dienophiles 25a and 25b in organic synthesis.