(1S,2S,4aS,5S,6S,8S,8aR)-4-Bromo-2-[(E)-3-(tert-butyl-dimethyl-silanyloxy)-1-methyl-propenyl]-5-methoxymethoxy-1,6,8-trimethyl-1,2,4a,5,6,7,8,8a-octahydro-naphthalene-1-carbaldehyde | 198289-33-7

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: (1S,2S,4aS,5S,6S,8S,8aR)-4-Bromo-2-[(E)-3-(tert-butyl-dimethyl-silanyloxy)-1-methyl-propenyl]-5-methoxymethoxy-1,6,8-trimethyl-1,2,4a,5,6,7,8,8a-octahydro-naphthalene-1-carbaldehyde
• 英文别名: (1S,2S,4aS,5S,6S,8S,8aR)-4-bromo-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
• CAS: 198289-33-7
• 化学式: C₂₆H₄₅BrO₄Si
• 分子量: 529.63
• InChiKey: HOONYUHYABXSGL-ITANZNRKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.97
• 重原子数：
  32
• 可旋转键数：
  9
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.81
• 拓扑面积：
  44.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (1S,2S,4aS,5S,6S,8S,8aR)-4-Bromo-2-[(E)-3-(tert-butyl-dimethyl-silanyloxy)-1-methyl-propenyl]-5-methoxymethoxy-1,6,8-trimethyl-1,2,4a,5,6,7,8,8a-octahydro-naphthalene-1-carbaldehyde 在 sodium amalgam 作用下， 以 甲醇 为溶剂， 以82%的产率得到(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：

  (2E,8Z,10E,12E)-(4S,6S,7S)-9-Bromo-14-(tert-butyl-dimethyl-silanyloxy)-7-methoxymethoxy-2,4,6,12-tetramethyl-tetradeca-2,8,10,12-tetraenal 在 2,6-二叔丁基-4-甲基苯酚 、 牛血清白蛋白 作用下， 以 甲苯 为溶剂， 反应 12.0h， 以90%的产率得到(1S,2S,4aS,5S,6S,8S,8aR)-4-Bromo-2-[(E)-3-(tert-butyl-dimethyl-silanyloxy)-1-methyl-propenyl]-5-methoxymethoxy-1,6,8-trimethyl-1,2,4a,5,6,7,8,8a-octahydro-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

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.