(1S,4R,4aR,5R,8S,9aS)-4a-((S)-Toluene-4-sulfinyl)-1,4,4a,5,8,9a-hexahydro-1,4;5,8-dimethano-anthraquinone | 187592-89-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 蒽
• 英文名称: (1S,4R,4aR,5R,8S,9aS)-4a-((S)-Toluene-4-sulfinyl)-1,4,4a,5,8,9a-hexahydro-1,4;5,8-dimethano-anthraquinone
• 英文别名: (1R,4R,5R,8S,9S,12S)-4-[(S)-(4-methylphenyl)sulfinyl]pentacyclo[10.2.1.15,8.02,11.04,9]hexadeca-2(11),6,13-triene-3,10-dione
• CAS: 187592-89-8
• 化学式: C₂₃H₂₀O₃S
• 分子量: 376.476
• InChiKey: CTEIMQFUOCRGSQ-YEIZRITOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  27
• 可旋转键数：
  2
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.39
• 拓扑面积：
  70.4
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (1S,4R,4aR,5R,8S,9aS)-4a-((S)-Toluene-4-sulfinyl)-1,4,4a,5,8,9a-hexahydro-1,4;5,8-dimethano-anthraquinone 以 乙酸乙酯 为溶剂， 反应 24.0h， 以75%的产率得到1α,4α,5β,8β-tetrahydro-1,4:5,8-dimethanoanthracene-9,10-dione
  参考文献：
  名称：

  (SS)-2-(p-Tolylsulfinyl)norborneno-p-benzoquinones:  A New Type of Facially Perturbed Enantiopure Quinones

  摘要：

  The syntheses and asymmetric Diels-Alder reactions of (SS)-2-(p-tolylsulfinyl)norboreno-p-benzoquinones 10 and 11 with cyclopentadiene are reported. The cycloadditions allowed the highly stereoselective obtention of the four possible endo adducts 12-15, optically pure synthetic equivalents of norborneno-p-benzoquinone-cyclopentadiene bisadducts. The detailed study of the H-1-NMR spectra of the adducts pointed out the anisotropic effects exerted by the sulfinyl moiety on the spectroscopic behavior of these rigid systems. In all cases, the pi-facial selectivities were fully controlled by the sulfinyl group being possible to reverse the diastereoselection in thermal conditions and in the presence of ZnBr2. The stereoselective synthesis of the cage compound 5, precursor of garudane, was achieved from cycloadduct endo-syn-13.

  DOI：

  10.1021/jo9618942
• 作为产物：
  描述：

  endo-<4aR,5S,8R,8aS,(S)S>-5,8-methano-2-(p-tolylsulfinyl)-4a,5,8,8a-tetrahydro-1,4-naphthoquinone 在 ammonium cerium(IV) nitrate 、 potassium carbonate 作用下， 以 四氢呋喃 、 二氯甲烷 、 水 、 乙腈 为溶剂， 反应 27.0h， 生成 (1S,4R,4aR,5R,8S,9aS)-4a-((S)-Toluene-4-sulfinyl)-1,4,4a,5,8,9a-hexahydro-1,4;5,8-dimethano-anthraquinone
  参考文献：
  名称：

  (SS)-2-(p-Tolylsulfinyl)norborneno-p-benzoquinones:  A New Type of Facially Perturbed Enantiopure Quinones

  摘要：

  The syntheses and asymmetric Diels-Alder reactions of (SS)-2-(p-tolylsulfinyl)norboreno-p-benzoquinones 10 and 11 with cyclopentadiene are reported. The cycloadditions allowed the highly stereoselective obtention of the four possible endo adducts 12-15, optically pure synthetic equivalents of norborneno-p-benzoquinone-cyclopentadiene bisadducts. The detailed study of the H-1-NMR spectra of the adducts pointed out the anisotropic effects exerted by the sulfinyl moiety on the spectroscopic behavior of these rigid systems. In all cases, the pi-facial selectivities were fully controlled by the sulfinyl group being possible to reverse the diastereoselection in thermal conditions and in the presence of ZnBr2. The stereoselective synthesis of the cage compound 5, precursor of garudane, was achieved from cycloadduct endo-syn-13.

  DOI：

  10.1021/jo9618942

文献信息

• (S<i>S</i>)-2-(<i>p</i>-Tolylsulfinyl)norborneno-<i>p</i>-benzoquinones:  A New Type of Facially Perturbed Enantiopure Quinones
  作者：M. Carmen Carreño、José L. García Ruano、Antonio Urbano、M. Isabel López-Solera

  DOI：10.1021/jo9618942

  日期：1997.2.1

  The syntheses and asymmetric Diels-Alder reactions of (SS)-2-(p-tolylsulfinyl)norboreno-p-benzoquinones 10 and 11 with cyclopentadiene are reported. The cycloadditions allowed the highly stereoselective obtention of the four possible endo adducts 12-15, optically pure synthetic equivalents of norborneno-p-benzoquinone-cyclopentadiene bisadducts. The detailed study of the H-1-NMR spectra of the adducts pointed out the anisotropic effects exerted by the sulfinyl moiety on the spectroscopic behavior of these rigid systems. In all cases, the pi-facial selectivities were fully controlled by the sulfinyl group being possible to reverse the diastereoselection in thermal conditions and in the presence of ZnBr2. The stereoselective synthesis of the cage compound 5, precursor of garudane, was achieved from cycloadduct endo-syn-13.