[(S)R]-4-hydroxy-4-[(p-tolylsulfinyl)methyl]-2,5-cyclohexadienone | 170117-33-6

• 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: [(S)R]-4-hydroxy-4-[(p-tolylsulfinyl)methyl]-2,5-cyclohexadienone
• 英文别名: [(S)R]-4-hydroxy-4-[p-(tolylsulfinyl)methyl]cyclohexa-2,5-dienone；[S(R)]-4-hydroxy-4-[(p-tolylsulfinyl)methyl]-2,5-cyclohexadienone；(SR)-4-hydroxy-4-[(p-tolylsulfinyl)methyl]cyclohexa-2,5-dienone；(R)-(p-tolulsulfinyl)methyl-p-quinol；4-hydroxy-4-[[(R)-(4-methylphenyl)sulfinyl]methyl]cyclohexa-2,5-dien-1-one
• CAS: 170117-33-6
• 化学式: C₁₄H₁₄O₃S
• 分子量: 262.329
• InChiKey: OLOAOMFBAOPUCS-GOSISDBHSA-N

物化性质

• 熔点：
  141-143 °C(Solv: ethyl acetate (141-78-6); hexane (110-54-3))
• 沸点：
  511.9±50.0 °C(Predicted)
• 密度：
  1.35±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  18
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.21
• 拓扑面积：
  73.6
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  [(S)R]-4-hydroxy-4-[(p-tolylsulfinyl)methyl]-2,5-cyclohexadienone 在 N-溴代丁二酰亚胺(NBS) 、 lithium carbonate 、 lithium bromide 作用下， 以 正己烷 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 8.5h， 生成 (R)-4-Ethyl-2-methyl-1-((R)-toluene-4-sulfinylmethyl)-cyclohexa-2,5-diene-1,4-diol
  参考文献：
  名称：

  Studies of Diastereoselectivity in Conjugate Addition of Organoaluminum Reagents to (R)-[(p-Tolylsulfinyl)methyl]quinols and Derivatives

  摘要：

  (R)-4-Hydroxy-4-[(p-tolylsulfinyl)methyl]-2,5-cyclohexadienones 1-3, and 6 reacted with organoaluminum derivatives from the pro-R conjugated position in a highly pi-facial diastereoselective manner directed by the C-4 OH. A similar facial diastereoselectivity arose from reactions with 3-alkyl-substituted analogues 4 and 5 and 5-alkyl-4-hydroxy-4-[(p-tolylsulfinyl)methyl]-2-cyclohexenones 10a,b. Semiempirical calculations (AM1 model) provide data on transition-state energies for additions in full agreement with the experimental results.

  DOI：

  10.1021/jo980084i
• 作为产物：
  描述：

  (R)-(+)-甲基对甲苯砜 在 正丁基锂 、 草酸 、 二异丙胺 作用下， 以 四氢呋喃 、 正己烷 、 水 为溶剂， 反应 2.0h， 生成 [(S)R]-4-hydroxy-4-[(p-tolylsulfinyl)methyl]-2,5-cyclohexadienone
  参考文献：
  名称：

  π-Facial Diastereoselection in Diels−Alder Reactions of (R)-4-[(p-Tolylsulfinyl)methyl]quinols

  摘要：

  Diels-Alder reactions of a range of (R)-4-hydroxy-4-[(p-tolylsulfinyl)methyl]-2,5-cyclohexadienones with cyclopentadiene and 1,3-pentadiene proceed in a total pi-facial diastereoselective manner from the C-4 OH side. Ab initio calculations at the RHF/6-31G* theory level provide data on transition-state energies for cycloadditions with cyclopentadiene in full agreement with the experimental results.

  DOI：

  10.1021/jo9712308

文献信息

• Stereocontrolled Approach to Phenyl Cyclitols from (<i>SR</i>)-[(<i>p</i>-Tolylsulfinyl)methyl]-<i>p</i>-quinol
  作者：Estíbaliz Merino、Rosanne P. A. Melo、Montserrat Ortega-Guerra、María Ribagorda、M. Carmen Carreño

  DOI：10.1021/jo900109p

  日期：2009.4.3

  Reactions of enantiopure (SR)-[(p-tolylsulfinyl)methyl]-p-quinol with ArAlMe2 reagents allowed a highly diastereoselective 1,4-addition of the aryl group with an efficient desymmetrization of the prochiral cyclohexadienone moiety. The asymmetric synthesis of phenyl-substituted polyoxygenated cyclohexane derivatives was achieved by combining this reaction with a stereoselective reduction and elimination

  对映纯（SR）-[（对甲苯磺酰亚胺基）甲基]-对苯二酚与ArAlMe 2试剂的反应可实现芳基的高度非对映选择性1,4-加成以及前手性环己二烯酮部分的高效去对称化。通过将该反应与氧化成砜后的立体选择性还原和消除β-羟基亚砜结合，以回收羰基并进行立体选择性环氧化，可以实现苯基取代的多氧化环己烷衍生物的不对称合成。
• Enantioselective Synthesis of (+)- and (−)-Dihydroepiepoformin and (+)-Epiepoformin
  作者：M. Carmen Carreño、Estíbaliz Merino、María Ribagorda、Álvaro Somoza、Antonio Urbano

  DOI：10.1021/ol050287a

  日期：2005.3.1

  [reaction: see text] The enantioselective synthesis of both enantiomers of dihydroepiepoformin (1) and (+)-epiepoformin (2) was achieved from (p-tolylsulfinyl)methyl-p-quinols (SR)- or (SS)-3 and (4R,SR)-4, respectively. Key features include the stereocontrolled conjugate addition of AlMe3 to p-quinol 3 and retrocondensation to the ketone functionality, previous to oxidation of the beta-hydroxy sulfoxide

  [反应：见正文]由（对-甲苯亚磺酰基）甲基-对苯二酚（SR）-或（SS）-3和（SS）-3和（4R，SR）-4。主要特征包括在将高级中间体的β-羟基亚砜部分氧化为相应的砜之前，将AlMe3立体控制地共轭添加到对苯二酚3中并逆缩成酮官能团。
• Enantioselective Synthesis of Natural Polyoxygenated Cyclohexanes and Cyclohexenes from [(p-Tolylsulfinyl)methyl]-p-quinols
  作者：M. Carmen Carreño、Estíbaliz Merino、María Ribagorda、Álvaro Somoza、Antonio Urbano

  DOI：10.1002/chem.200601330

  日期：2007.1.22

  present in a number of enantiomerically pure (SR)- and (SS)-[(p-tolylsulfinyl)methyl]-p-quinols allowed chemo- and stereocontrolled conjugate additions of different organoaluminium reagents to the cyclohexadienone moiety. The same fragment was also shown to act as an efficient chiral masking carbonyl group, after oxidation to sulfone and retroaddition in basic medium, with elimination of methyl p-tolyl

  对存在于许多对映体纯的（SR）-和（SS）-[（（对-甲苯基亚磺酰基）甲基]-对-喹诺醇中的β-羟基亚砜片段的利用允许将不同的有机铝试剂化学和立体控制的共轭加成到环己二烯酮部分上。在氧化为砜并在碱性介质中逆向加成并消除了甲基对甲苯基砜之后，该片段还显示出可作为有效的手性掩蔽羰基的基团。通过将这两种转化用作关键步骤，可对不同天然产物进行对映体控制的合成，例如二氢表二甲双胍，（-）-葡糖胺O，（+）-表二甲双胍，（-）-可可生物碱和（+）-4-的两种对映体现已实现了表没食子碱A（一种天然产物菜黄素A的差向异构体）。β-羟基砜部分的存在使环状结构变得刚性，在到达天然结构的过程中，可以进行许多立体选择性转化，例如羰基还原，烯酮环氧化或顺式二羟基化。观察到的选择性取决于每个底物中的特定取代基，提供了远端基团对反应物优选的反应构象的优选方法的强烈影响的证据。还合成了天然（+）-harveynone的高
• Synthesis of Azobenzenes from Quinone Acetals and Arylhydrazines
  作者：M. Carmen Carreño、Gerardo Fernández Mudarra、Estíbaliz Merino、María Ribagorda

  DOI：10.1021/jo0498011

  日期：2004.5.1

  Direct reaction between quinone bisacetals and arylhydrazines gives azobenzenes. The presence of catalytic amounts of cerium ammonium nitrate strongly accelerates the reaction. When the bisacetal has a substituent at the 2,5-cyclohexadiene framework, only one regioisomer is formed. The method represents a simple, mild, and novel synthetic access to differently substituted azocompounds in high to excellent

  醌双缩醛与芳基肼之间的直接反应生成偶氮苯。催化量的硝酸铈铵铵的存在强烈地促进了反应。当双缩醛在2，5-环己二烯骨架上具有取代基时，仅形成一种区域异构体。该方法代表了一种简单，温和且新颖的合成方法，可以高收率地获得不同取代的偶氮化合物。
• Synthesis and diels-alder reactions of (R)-4-hydroxy-4-p-tolylsulfinylmethyl-2,5-cyclohexadienone
  作者：M.Carmen Carreño、Manuel Pérez González、Jean Fischer

  DOI：10.1016/0040-4039(95)00879-h

  日期：1995.7

  Enantiomerically pure (R)-4-hydroxy-4-p-tolylsulfinylmethyl-2,5-cyclohexadienone 1 was synthesized in two steps and 80% overall yield from 4,4-dimethoxy-2,5-cyclohexadienone and (R)-methyl-p-tolyl sulfoxide. The Diels-Alder reaction of cyclopentadiene with 1 ocurred exclusively from the C-4 hydroxyl face in either thermal or catalytic conditions. From the reaction carried out in the presence of BF3·OEt2

  对映体纯的（R）-4-羟基-4-对甲苯基亚磺酰基甲基-2,5-环己二烯酮1分两步合成，并且从4,4-二甲氧基-2,5-环己二烯酮和（R）-甲基的总收率达到80％-对甲苯基亚砜。环戊二烯与1的Diels-Alder反应仅在热或催化条件下发生于C-4羟基表面。从在-78℃下在BF 3 ·OEt 2存在下进行的反应中，以75％的收率分离出加合物6。