endo-<4aR,5S,8R,8aS,(S)S>-5,8-methano-2-(p-tolylsulfinyl)-4a,5,8,8a-tetrahydro-1,4-naphthoquinone | 162060-46-0

• 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: endo-<4aR,5S,8R,8aS,(S)S>-5,8-methano-2-(p-tolylsulfinyl)-4a,5,8,8a-tetrahydro-1,4-naphthoquinone
• 英文别名: (4aR,5S,8R,8aS,S_S)-5,8-methano-2-p-tolylsulfinyl-4a,5,8,8a-tetrahydro-1,4-naphthoquinone；(+)-(1S,4R,4aS,8aR)-6-((S)-p-tolylsulfinyl)-1,4,4a,8a-tetrahydro-1,4-methanonaphthalene-5,8-dione；(1R,2S,7R,8S)-4-[(S)-(4-methylphenyl)sulfinyl]tricyclo[6.2.1.02,7]undeca-4,9-diene-3,6-dione
• CAS: 162060-46-0
• 化学式: C₁₈H₁₆O₃S
• 分子量: 312.389
• InChiKey: MKHWZKPAEPKHIA-XFPXYBLMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  22
• 可旋转键数：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.33
• 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：

  endo-<4aR,5S,8R,8aS,(S)S>-5,8-methano-2-(p-tolylsulfinyl)-4a,5,8,8a-tetrahydro-1,4-naphthoquinone 在 titanium(III) chloride 、 ammonium cerium(IV) nitrate 、 potassium carbonate 、 zinc dibromide 作用下， 以 四氢呋喃 、 水 、 丙酮 、 乙腈 为溶剂， 反应 5.5h， 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：

  2-(p-tolylthio)cyclohexa-2,5-diene-1,4-dione 在 间氯过氧苯甲酸 作用下， 以 二氯甲烷 为溶剂， 反应 3.0h， 生成 endo-<4aR,5S,8R,8aS,(S)S>-5,8-methano-2-(p-tolylsulfinyl)-4a,5,8,8a-tetrahydro-1,4-naphthoquinone
  参考文献：
  名称：

  Influence of the Sulfinyl Group on the Chemoselectivity and π-Facial Selectivity of Diels−Alder Reactions of (S)-2-(p-Tolylsulfinyl)-1,4-benzoquinone

  摘要：

  Diels-Alder reactions of (S)-2-(p-tolylsulfinyl)-1,4-benzoquinone (1a) with cyclic (cyclopentadiene and cyclohexadiene) and acyclic dienes (1-[(trimethylsilyl)oxy]-1,3-butadiene and trans-piperylene) under different thermal and Lewis acid conditions are reported. Chemoselectivity (reactions on C-2-C-3 versus C-5-C-6 double bonds) is mainly related to the cyclic (on C-5-C-6) or acyclic (on C-2-C-3) structure of the diene. The high pi-facial selectivity observed could be controlled by choosing adequate experimental conditions.

  DOI：

  10.1021/jo951438y

文献信息

• Diels−Alder Reactions with 2-(Arylsulfinyl)-1,4-benzoquinones:  Effect of Aryl Substitution on Reactivity, Chemoselectivity, and π-Facial Diastereoselectivity
  作者：M. Carmen Carreño、José L. García Ruano、Antonio Urbano、Cynthia Z. Remor、Yolanda Arroyo

  DOI：10.1021/jo9913107

  日期：2000.1.1

  Eu(fod)(3)- or BF(3).OEt(2)-catalyzed conditions. The synthesis of endo-adduct [4aS,5S,8R,8aR,SS]-9d resulting from cycloaddition on the substituted C(2)-C(3) double bond was achieved in a chemo- and diastereoselective way from quinone 1d in the presence of ZnBr(2). The reactivity and selectivity of the process proved to be dependent on the electron density of the arylsulfinyl group.

  （SS）-2-（2'-甲氧基萘亚磺酰基）-1、4-苯醌（1b），2-（对甲氧基苯基亚磺酰基）-1,4-苯醌（1c）和2-（对-苯基据报道，硝基苯基亚磺酰基）-1,4-苯醌（1d）与环戊二烯。这些环加成反应使非对映异构体内加合物具有高度化学和立体选择性，这是由在热和Eu（fod）（3）-或BF（ 3）.OEt（2）催化的条件。在取代的C（2）-C（3）双键上通过环加成反应制得的内加合物[4aS，5S，8R，8aR，SS] -9d是通过化学和非对映选择性的方式从醌1d中合成的ZnBr（2）的存在。事实证明，该方法的反应性和选择性取决于芳基亚磺酰基的电子密度。
• Synthesis and asymmetric diels-alder reactions of (S)-2-p-tolylsulfinyl-1,4-benzoquinone
  作者：M.Carmen Carreño、Jose L Garcia Ruano、Antonio Urbano

  DOI：10.1016/s0040-4039(00)99307-9

  日期：1989.1

  Optically pure (S)-2-p-tolylsulfinyl-1,4-benzoquinone (5) is readily obtained by deketalization of the corresponding quinone bisketal 4, synthesized by Andersen's type synthesis on 2-bromo-1,4-dimethoxybenzene (1) followed by anodic oxidation of the resulting sulfoxide. The Diels-Alder reaction of cyclopentadiene with 5 took place on C5-C6 dienophilic double bond showing high facial selectivity, which can

  光学上纯净的（S）-2-对甲苯基亚磺酰基-1,4-苯醌（5）可通过相应的醌双缩酮4的缩酮化反应轻松获得，该缩酮是通过安徒生式合成方法在2-溴-1,4-二甲氧基苯上合成的（1）然后将所得亚砜进行阳极氧化。环戊二烯与5的Diels-Alder反应发生在C 5 -C 6双亲双键上，显示出高的面部选择性，可以通过使用不同的路易斯酸和总内向选择性将其反转。
• Studies of Diastereoselectivity in Diels−Alder Reactions of (S)<i>S</i>-4a,5,8,8a-Tetrahydro-5,8-methane-2-(<i>p</i>-tolylsulfinyl)-1,4-naphtho- quinones with Cyclopentadiene
  作者：M. Carmen Carreño、José L. García Ruano、Antonio Urbano、Miguel A. Hoyos

  DOI：10.1021/jo9521209

  日期：1996.1.1

  compounds 6 and 7 have proved to be adequate rigid models to evaluate the ability of the sulfinyl group to control the diastereoselectivity of the [4 + 2] cycloadditions of cyclopentadiene on the ene-dione moiety. The results of thermal and Lewis acid-catalyzed reactions allowed us to establish that both reactivity and endo/exo selectivity were modulated by the presence of the sulfinyl group, the endo-anti-endo

  标题化合物6和7已被证明是适当的刚性模型，可用于评估亚磺酰基控制在烯二酮部分上环戊二烯的[4 + 2]环加成的非对映选择性。热和路易斯酸催化反应的结果使我们能够确定，亚砜基的存在可调节反应性和内/外选择性，内-反-内或外-反-内双加合物是主要的产品取决于实验条件。使用了SOTol基团与几种路易斯酸（BF（3）.OEt（2），Eu（fod）（3），ZnBr（2））之间的缔合作用，该位移移位了CS键周围的构象平衡解释主要受空间因素控制的环加成反应的立体化学过程。
• 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％。
• The Diels-Alder reaction of 1,4-quinones in hexafluoroisopropanol
  作者：Loïc Jeanmart、Kalina Mambourg、Gilles Hanquet、Steve Lanners

  DOI：10.24820/ark.5550190.p012.140

  日期：——