methyl (2R,4aR,5S,8aS)-7-formyl-5-hydroxy-2-phenyl-4,4a,5,8-tetrahydro-1,3-benzodioxine-8a-carboxylate | 198289-40-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二恶烷
• 英文名称: methyl (2R,4aR,5S,8aS)-7-formyl-5-hydroxy-2-phenyl-4,4a,5,8-tetrahydro-1,3-benzodioxine-8a-carboxylate
• CAS: 198289-40-6
• 化学式: C₁₇H₁₈O₆
• 分子量: 318.326
• InChiKey: AJSLYOOERGHWPS-DLTWYDFYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.6
• 重原子数：
  23
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.41
• 拓扑面积：
  82.1
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  methyl (2R,4aR,5S,8aS)-7-formyl-5-hydroxy-2-phenyl-4,4a,5,8-tetrahydro-1,3-benzodioxine-8a-carboxylate 在 咪唑 、 sodium tetrahydroborate 、 cerium(III) chloride 、 mercury(II) diacetate 、 水 、 N,N-二异丙基乙胺 作用下， 以 甲醇 、 二氯甲烷 、 溶剂黄146 、 N,N-二甲基甲酰胺 为溶剂， 反应 55.5h， 生成 methyl (1S,5S,6R)-3-[[tert-butyl(diphenyl)silyl]oxymethyl]-6-(ethenoxymethyl)-1-hydroxy-5-(methoxymethoxy)cyclohex-3-ene-1-carboxylate
  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：

  2,4-己二炔-1,6-二醇 在 咪唑 、 草酰氯 、 2,6-二叔丁基-4-甲基苯酚 、 碳酸氢钠 、 potassium carbonate 、 triethylamine tris(hydrogen fluoride) 、 间氯过氧苯甲酸 、 红铝 、 zinc(II) chloride 作用下， 以 四氢呋喃 、 乙醚 、 二氯甲烷 、 二甲基亚砜 、 三乙胺 、 N,N-二甲基甲酰胺 、 甲苯 、 乙腈 为溶剂， 反应 147.0h， 生成 methyl (2R,4aR,5S,8aS)-7-formyl-5-hydroxy-2-phenyl-4,4a,5,8-tetrahydro-1,3-benzodioxine-8a-carboxylate
  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.