(S)-(+)-N-(p-cyanobenzylidene)-p-toluenesulfinamide | 503819-65-6

• 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)-(+)-N-(p-cyanobenzylidene)-p-toluenesulfinamide
• 英文别名: (NE,S)-N-[(4-cyanophenyl)methylidene]-4-methylbenzenesulfinamide
• CAS: 503819-65-6
• 化学式: C₁₅H₁₂N₂OS
• 分子量: 268.339
• InChiKey: NTKYAQWLSDVLLQ-OXRZLYTFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  19
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.07
• 拓扑面积：
  72.4
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (S)-2-(Triisopropylsyloxymethyl)phenyl p-tolylsulfoxide 、 (S)-(+)-N-(p-cyanobenzylidene)-p-toluenesulfinamide 在 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 1.0h， 以74%的产率得到[1R,2S,(S)S]-N-{1-(4-cyanophenyl)-2-[(S)-2-(p-toluenesulfinyl)phenyl]-2-triisopropylsilanyloxyethyl}-p-toluenesulfinamide
  参考文献：
  名称：

  Stereocontrolled Reactions Mediated by a Remote Sulfoxide Group:  Synthesis of Optically Pure anti-β-Amino Alcohols

  摘要：

  A one-step synthesis of enantiomerically pure anti-1,2-amino alcohol derivatives has been achieved by reaction of prochiral oxygenated 2-p-tolylsulfinylbenzyl carbanions with N-sulfinylimines bearing the same configuration at sulfur.

  DOI：

  10.1021/ol0358410
• 作为产物：
  描述：

  4-氰基苯甲醛 、 (S)-(+)-对甲基苯亚磺酰胺 在 ytterbium(III) triflate 作用下， 以 四氢呋喃 为溶剂， 反应 12.0h， 以91%的产率得到(S)-(+)-N-(p-cyanobenzylidene)-p-toluenesulfinamide
  参考文献：
  名称：

  Synthesis of Enantiopure Sulfinimines (Thiooxime S-Oxides) Catalyzed by Yb(OTf)₃ from p-Toluenesulfinamide and Aldehydes in Mild Reaction Conditions

  摘要：

  Enantiomerically pure sulfinimines as important building blocks in the asymmetric synthesis of amine derivatives are prepared in good to excellent yields from chiral p-toluenesulfinamide with aromatic, heteroaromatic, and aliphatic aldehydes. The unprecedented feature of the reported procedure is that the formation of the sulfinimines was achieved by the catalytic action of Yb(OTf)(3) in THF at room temperature. The reaction conditions were also applicable to Ellman's sulfinimines.

  DOI：

  10.1021/jo048597e

文献信息

• Asymmetric Aza-Henry Reactions from <i>N</i>-<i>p</i>-Tolylsulfinylimines
  作者：José Luis García Ruano、Markus Topp、Jesús López-Cantarero、José Alemán、Modesto J. Remuiñán、M. Belén Cid

  DOI：10.1021/ol051580d

  日期：2005.9.1

  [reaction: see text] N-Sulfinylimines derived from aromatic or aliphatic aldehydes and ketones react with nitromethane and NaOH in a highly diastereoselective manner under mild conditions. In the presence of TBAF, the reaction rates are strongly increased and the stereoselectivity is inverted. This method provides enantiomerically pure beta-nitroamines derived from enolizable aldimines and ketimines

  [反应：见正文]在温和条件下，衍生自芳族或脂族醛和酮的N-亚磺酰亚胺与硝基甲烷和NaOH以高度非对映选择性的方式反应。在TBAF的存在下，反应速率大大提高并且立体选择性反转。该方法提供了对映体纯的β-硝基胺，其衍生自可烯醇化的亚胺和酮亚胺，到目前为止，氮杂-亨利反应很难获得。
• 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。
• Preparation of α-amino ketones, β-amino hydroxylamines using asymmetric aza-Henry reactions of N-p-tolylsulfinylimines with nitroethane
  作者：José Luis García Ruano、Jesús López-Cantarero、Teresa de Haro、José Alemán、M. Belén Cid

  DOI：10.1016/j.tet.2006.10.021

  日期：2006.12

  N-Sulfinylimines derived from aromatic and aliphatic aldehydes react with nitroethane and NaOH, yielding mainly two diastereoisomeric β-nitroamines as the result of a highly diastereoselective reaction and further epimerization of the carbon linked to the nitro group. The resulting β-nitroamines are used as precursors of N-sulfonyl α-amino methyl ketones and β-amino hydroxylamines.

  衍生自芳族和脂族醛的N-亚磺酰亚胺与硝基乙烷和NaOH反应，由于高度非对映选择性反应和与硝基相连的碳进一步差向异构化，因此主要生成两种非对映异构体β-硝基胺。所得的β-硝基胺用作N-磺酰基α-氨基甲基酮和β-氨基羟胺的前体。
• 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
• Stereocontrolled Reactions Mediated by a Remote Sulfoxide Group:  Synthesis of Optically Pure <i>a</i><i>nti</i>-β-Amino Alcohols
  作者：José L. García Ruano、José Alemán

  DOI：10.1021/ol0358410

  日期：2003.11.1

  A one-step synthesis of enantiomerically pure anti-1,2-amino alcohol derivatives has been achieved by reaction of prochiral oxygenated 2-p-tolylsulfinylbenzyl carbanions with N-sulfinylimines bearing the same configuration at sulfur.