(5S,8R,SS)-5,8-methano-2-p-tolylsulfinyl-5,8-dihydro-1,4-naphthoquinone | 161953-70-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (5S,8R,SS)-5,8-methano-2-p-tolylsulfinyl-5,8-dihydro-1,4-naphthoquinone
• 英文别名: (1R,8S)-4-[(S)-(4-methylphenyl)sulfinyl]tricyclo[6.2.1.02,7]undeca-2(7),4,9-triene-3,6-dione
• CAS: 161953-70-4
• 化学式: C₁₈H₁₄O₃S
• 分子量: 310.373
• InChiKey: AYVRQLKXJDORPZ-DMDKVIGKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  22
• 可旋转键数：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.22
• 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：

  (5S,8R,SS)-5,8-methano-2-p-tolylsulfinyl-5,8-dihydro-1,4-naphthoquinone 在 titanium(III) chloride 、 zinc dibromide 作用下， 以 丙酮 为溶剂， 反应 2.5h， 生成 syn-9,10-dihydroxy-(1α,4α,5α,8α)-1,4,5,8-tetrahydro-1,4:5,8-dimethanoanthracene
  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， 生成 (5S,8R,SS)-5,8-methano-2-p-tolylsulfinyl-5,8-dihydro-1,4-naphthoquinone
  参考文献：
  名称：

  （S）-3-氯和（S）-3-乙基-2-对甲苯基亚磺酰基-1,4-苯醌的合成和狄尔斯-阿尔德反应

  摘要：

  描述了对映体纯形式的标题化合物的合成。在ZnBr 2的存在下，它们与环戊二烯和2,3-二甲基-1,3-丁二烯的环加成反应发生在未取代的双亲双键C 5 -C 6上，从而获得具有旋光性的4a，5,8,8a-四氢萘醌非对映异构体过量为40％至72％。

  DOI：

  10.1016/0040-4039(94)88379-3

文献信息

• Synthesis and diels-alder reactions of (S)-3-chloro and (S)-3-ethyl-2-p-tolylsulfinyl-1,4-benzoquinones
  作者：M.Carmen Carreño、José L.García Ruano、Miguel A. Toledo、Antonio Urbano

  DOI：10.1016/0040-4039(94)88379-3

  日期：1994.12

  The synthesis of the title compounds in enantiomerically pure form is described. Their cycloadditions with cyclopentadiene and 2,3-dimethyl-1,3-butadiene in the presence of ZnBr2 take place on the unsubstituted dienophilic double bond C5-C6 giving access to optically active 4a,5,8,8a-tetrahydronaphthoquinones with a diastereoisomeric excess ranging from 40 to 72%.

  描述了对映体纯形式的标题化合物的合成。在ZnBr 2的存在下，它们与环戊二烯和2,3-二甲基-1,3-丁二烯的环加成反应发生在未取代的双亲双键C 5 -C 6上，从而获得具有旋光性的4a，5,8,8a-四氢萘醌非对映异构体过量为40％至72％。
• (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.