(S)-α-methylthio-2-(p-tolylsulfinyl)toluene | 852332-84-4

• 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: (S)-α-methylthio-2-(p-tolylsulfinyl)toluene
• 英文别名: Benzene, 1-[(S)-(4-methylphenyl)sulfinyl]-2-[(methylthio)methyl]-；1-[(S)-(4-methylphenyl)sulfinyl]-2-(methylsulfanylmethyl)benzene
• CAS: 852332-84-4
• 化学式: C₁₅H₁₆OS₂
• 分子量: 276.423
• InChiKey: GVPJVJFIUVEWQU-SFHVURJKSA-N

物化性质

• 沸点：
  444.3±38.0 °C(Predicted)
• 密度：
  1.23±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  18
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  61.6
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (S)-α-methylthio-2-(p-tolylsulfinyl)toluene 在 三氟乙酸 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 甲醇 、 正己烷 为溶剂， 反应 0.08h， 生成 (1R)-1-benzylpentylamine
  参考文献：
  名称：

  Synthesis of Optically Pure 1,2-Diaryl- and 1,2-Alkylaryl-1,2-amino Sulfides

  摘要：

  The reactions of the lithium (S)-alpha-(methylthio)-2-(p-toluenesulfinyl)benzyl carbanion with (S)-N-p-tolylsulfinyl aldimines evolve in a completely stereoselective manner providing a one-step synthesis of enantiomerically pure anti-1,2-disubstituted 1,2-amino sulfide derivatives.

  DOI：

  10.1021/jo050129x
• 作为产物：
  描述：

  二甲基二硫 、 (S)-1-methyl-2-(p-tolylsulfinyl)benzene 在 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 0.5h， 以70%的产率得到(S)-α-methylthio-2-(p-tolylsulfinyl)toluene
  参考文献：
  名称：

  Synthesis of Optically Pure 1,2-Diaryl- and 1,2-Alkylaryl-1,2-amino Sulfides

  摘要：

  The reactions of the lithium (S)-alpha-(methylthio)-2-(p-toluenesulfinyl)benzyl carbanion with (S)-N-p-tolylsulfinyl aldimines evolve in a completely stereoselective manner providing a one-step synthesis of enantiomerically pure anti-1,2-disubstituted 1,2-amino sulfide derivatives.

  DOI：

  10.1021/jo050129x

文献信息

• Optically pure trans-2,3-disubstituted N-sulfinyl aziridines. Regio- and stereoselective opening mediated by the sulfinyl group
  作者：Yolanda Arroyo、Ángela Meana、J. Félix Rodríguez、Mercedes Santos、M. Ascensión Sanz-Tejedor、José L. García-Ruano

  DOI：10.1016/j.tet.2006.06.072

  日期：2006.9

  A new entry to optically pure trans-2,3-disubstituted N-sulfinyl aziridines starting from 1,2-aminosulfides, involving formation of a sulfonium salt intermediate followed by intramolecular nucleophilic attack by the sulfinamide nitrogen atom, is reported. The regio- and stereoselective opening of the aziridine ring can be achieved by anchimeric assistance of the sulfinyl group.

  据报道，从1，2-氨基硫化物开始的光学纯的反式-2，3-二取代的N-亚磺酰基氮丙啶的新进入，涉及形成salt盐中间体，然后由亚磺酰胺氮原子进行分子内亲核攻击。氮丙啶环的区域和立体选择性开放可通过亚磺酰基的嵌合辅助来实现。
• Stereoselective Control of Planar α-Dimethylsulfonium Benzyl Carbanions. Synthesis of Optically Pure <i>trans</i>-Aziridines
  作者：Yolanda Arroyo、Ángela Meana、J. Félix Rodríguez、M. Ascensión Sanz-Tejedor、Inés Alonso、José L. García Ruano

  DOI：10.1021/jo900381b

  日期：2009.6.5

  (R)-N-Sulfinylimine and (S)-N-sulfinylimine react with the ylide derived from (S)-dimethyl-[2-(p-toluenesulfinyl)phenyl]sulfonium salt, affording trans-2,3-disubstituted aziridines. A complete trans selectivity in low facial diastereoselectivity is observed when the configuration at the sulfur atoms of the reagents is the same. Otherwise, when their configurations are different, the reaction evolved

  （R）-N-亚磺酰亚胺和（S）-N-亚磺酰亚胺与衍生自（S）-二甲基-[2-（对甲苯亚磺酰基）苯基] ulf盐的叶立德反应，得到反式-2,3-二取代的氮丙啶。当试剂的硫原子处的构型相同时，可以观察到低的非对映选择性的完全反式选择性。否则，当它们的构型不同时，反应会随着面部总非对映选择性和顺/反式而发展。比率介于1 / 4.2和1/9之间。理论计算表明反应主要是通过平面自由碳负离子的演化而进行的。过渡态的相对稳定性预测反式/顺式比与实验结果非常吻合。
• Synthesis of Optically Pure <i>vic</i>-Sulfanyl Amines Mediated by a Remote Sulfinyl Group
  作者：Yolanda Arroyo、M. Ascensión Sanz-Tejedor、Inés Alonso、José L. García-Ruano

  DOI：10.1021/ol201696y

  日期：2011.9.2

  Enantiomerically pure syn-1,2-diaryl-1,2-sulfanylamine derivatives can be obtained in a completely stereoselective manner by reaction of the benzylcarbanion Li-(S)-1 with N-phenyl (or PMP)-arylidene aldimines and further desulfinylation with t-BuLi. Theoretical studies at the DFT (mPW1PW91) level with the CPCM model, by using the Gaussian09 program, provide a good explanation for the stereochemical results.
• A New Access to the Synthesis of Optically Pure β-Aminosulfides
  作者：Y. Arroyo、A. Meana、J. F. Rodríguez、M. Santos、M. A. Sanz-Tejedor、J. L. García Ruano

  DOI：10.1080/10426500590913320

  日期：2005.3.2
• Stereoselective Addition of α-Methylsulfenyl Benzyl Carbanions to <i>N</i>-Sulfinylketimines: Asymmetric Synthesis of α,α-Dibranched β-Sulfanyl Amines
  作者：Yolanda Arroyo、Ángela Meana、M. Ascensión Sanz-Tejedor、Inés Alonso、José L. García Ruano

  DOI：10.1021/jo802200f

  日期：2009.1.16

  (R)- and (S)-N-sulfinylketimines react with the ortho-sulfinyl benzyl carbanion derived from (S)-1 affording epimeric mixtures at the benzylic carbon of alpha,alpha-dibranched beta-sulfanyl amines. The N-sulfinyl group completely controls the configuration at the quaternary carbon bonded to the nitrogen, whereas the C-sulfinyl group is responsible for the level of asymmetric induction. High stereoselectivity can be achieved when the configuration at the sulfur atoms of the reagents are opposite (matched pair). After a two-step desulfinylation process, this reaction provides a procedure for synthesizing diastereomerically pure syn-1,2-sulfanyl amines containing a chiral quaternary carbon adjacent to nitrogen.