(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 | 138194-43-1

• 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)-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: 138194-43-1
• 化学式: C₂₆H₄₆O₄Si
• 分子量: 450.734
• InChiKey: FEPWDPNJNOIQCJ-DBEFIKIESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.24
• 重原子数：
  31
• 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)-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 在 n-Pr₄RuO₄ N-氯代丁二酰亚胺 、 N-甲基吲哚酮 、 二甲基硫 、 氢氟酸 、 叔丁基锂 、 4-甲基苯磺酸吡啶 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 、 乙腈 为溶剂， 反应 35.17h， 生成
  参考文献：
  名称：

  四环素，四环素的糖苷配基的全合成

  摘要：

  通过螺环膦酸酯3与八氢萘醛17的偶联以及随后的ω-砜-α-醛2的大环化，已经实现了tetronolide（1）的首次全合成，从而确定了1的绝对构型。

  DOI：

  10.1016/s0040-4039(00)93498-1
• 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-tetraen-1-ol 在 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 、 牛血清白蛋白 作用下， 以 甲醇 、 二氯甲烷 、 甲苯 为溶剂， 反应 12.17h， 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

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.
• Total synthesis of tetronolide, the aglycon of tetrocarcins
  作者：Kei Takeda、Eiji Kawanishi、Hitoshi Nakamura、Eiichi Yoshii

  DOI：10.1016/s0040-4039(00)93498-1

  日期：1991.9

  The first total synthesis of tetronolide (1) has been achieved via coupling of spirotetronate 3 with octahydronaphthalene aldehyde 17 and subsequent macrocyclization of ω-sulfone-α-aldehyde 2, leading to confirmation of the absolute configuration of 1.

  通过螺环膦酸酯3与八氢萘醛17的偶联以及随后的ω-砜-α-醛2的大环化，已经实现了tetronolide（1）的首次全合成，从而确定了1的绝对构型。