(S)-(+)-N-(butylidene)-p-toluenesulfinamide | 161123-25-7

• 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-(butylidene)-p-toluenesulfinamide
• 英文别名: (S)-(+)-N-butylidiene-p-toluenesulfinamide；(S)-N-butylidene-4-methylbenzenesulfinamide
• CAS: 161123-25-7
• 化学式: C₁₁H₁₅NOS
• 分子量: 209.312
• InChiKey: MNFLNNSREQPEIF-AWEZNQCLSA-N

物化性质

• 沸点：
  348.7±35.0 °C(predicted)
• 密度：
  1.08±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.89
• 重原子数：
  14.0
• 可旋转键数：
  4.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  29.43
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  (S)-(+)-N-(butylidene)-p-toluenesulfinamide 在 正丁基锂 、 sodium hexamethyldisilazane 、 二异丙胺 、 lithium chloride 作用下， 以 四氢呋喃 、 乙醚 、 正己烷 为溶剂， 反应 2.67h， 生成 (2S,3S)-(+)-methyl 2-methyl-3-[(S)-(4-methylphenylsulfinamido)]hexanoate
  参考文献：
  名称：

  Asymmetric Synthesis of anti-α-Substituted β-Amino Ketones from Sulfinimines

  摘要：

  Previously unknown, enantiopure, beta-amino ketones were prepared in modest yield by addition of lithium reagents to N-sulfinyl anti-alpha-substituted beta-amino Weinreb amides. Grignard reagents failed to add to these Weinreb amides in contrast to the syn-alpha-substituted isomers which did. The anti-alpha-substituted beta-amino Weinreb amides were prepared by addition of LiN(OMe)Me to the corresponding N-sulfinyl anti-alpha-substituted beta-amino esters because alpha-alkylation of N-sulfinyl beta-amino Weinreb amide enolates resulted in poor diastereoselectivities.

  DOI：

  10.1021/jo2002352
• 作为产物：
  描述：

  正丁醛 、 (S)-(+)-对甲基苯亚磺酰胺 在 4-甲基苯磺酸吡啶 、 magnesium sulfate 作用下， 以 二氯甲烷 为溶剂， 反应 24.0h， 以58%的产率得到(S)-(+)-N-(butylidene)-p-toluenesulfinamide
  参考文献：
  名称：

  通过亚甲基环丙基酰胺的碘化物介导的选择性扩环合成高度官能化的吡咯烷。

  摘要：

  该手稿描述了一种高度选择性的碘化物介导的串联曼尼希/环化反应，可从亚甲基环丙基酰胺获得反式-2,3-二取代的吡咯烷，并具有良好的产率和选择性。反应范围已大大扩大，包括各种各样的芳族，杂芳族和α，β-不饱和亚胺，以及各种亚甲基环丙基酰胺。另外，进行了机械研究，以确定使用氘代底物的开环/闭环机理的性质。这些研究的结果表明，其主要机制是S（N）2 / S（N）2开环/闭环，并且碘或碘化物介导的碘烯醇酸酯异构化很可能发生。

  DOI：

  10.1021/jo802049u

文献信息

• Zinc-mediated Coupling Reaction of 2-Bromo-2,3,3,3-tetrafluoropropanoate with Various Chiral Imines. Simple and Effective Access to Optically Active α-Fluoro-α-(trifluoromethyl)-β-amino Esters
  作者：Takashi Sekiguchi、Kei Sato、Takashi Ishihara、Tsutomu Konno、Hiroki Yamanaka

  DOI：10.1246/cl.2004.666

  日期：2004.6

  The reactions of benzyl 2-bromo-2,3,3,3-tetrafluoropropanoate with various types of chiral imines in the presence of zinc in THF at room temperature were revealed to afford the threo- and erythro-isomers of α-fluoro-α-(trifluoromethyl)-β-amino esters with high diasteremeric excesses in fair to good chemical yields.

  在锌存在下，2-溴-2,3,3,3-四氟丙酸苄酯与各种手性亚胺在室温下于四氢呋喃中的反应显示，可以得到α-氟-α-（三氟甲基）-β-氨基酯的三氟异构体和赤氟异构体，非对映过量较高，化学收率尚可。
• Stereocontrolled Addition of Scrambling <i>ortho</i>-Sulfinyl Carbanions: Easy Access to Homopropargylamines and α-Allenylamines
  作者：Balú Cruz-Delgado、Ricardo I. Rodríguez、Anielka Rosado-Abón、Rubén Sánchez-Obregón、Francisco Yuste、José Alemán

  DOI：10.1021/acs.orglett.0c00625

  日期：2020.3.20

  An unprecedented behavior of ortho-sulfinylpropargyl carbanions in the presence of optically active sulfinylimines affords two different families of compounds: this peculiar chemodivergency is importantly affected by the nature of the employed base, and assisted by the configuration of the electrophile, displaying no alteration in the stereocontrol of both reactions. alpha-Allenylamines are formed exclusively, using R-sulfinyl aldimines as electrophiles, while homopropargylamines result when S-sulfinyl aldimines are employed.
• Synthesis of Optically Pure 1,2-Diaryl- and 1,2-Alkylaryl-1,2-amino Sulfides
  作者：Yolanda Arroyo、Ángela Meana、J. Félix Rodríguez、Mercedes Santos、M. Ascensión Sanz-Tejedor、José. L. García Ruano

  DOI：10.1021/jo050129x

  日期：2005.5.1

  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.
• Synthesis of Enantiomerically Pure <i>anti</i>-1,2-Diaryl and <i>syn</i>-1,2-Alkylaryl <i>vic</i>-Selenoamines
  作者：José L. García Ruano、Esther Torrente、Inés Alonso、Mercedes Rodriguez、Ana M. Martín-Castro、Alessandro Degl’Innocenti、Lucrezia Frateschi、Antonella Capperucci

  DOI：10.1021/jo202611v

  日期：2012.2.17

  Phenylselenyl benzylcarbanion stabilized by an (S)-2-p-tolylsulfinyl group evolves in a highly stereoselective way in the reactions with (S)-N-(p-tolylsulfinyl)imines at -98 degrees C affording diastereomerically pure 1,2-selenoamino derivatives in good yields. The syn or anti relationship of the obtained compounds depends on the alkyl or aryl character of the imine. They are easily transformed into enantiomerically pure (1R,2S)-1-aryl [or (1S,2S)-1-alkyl]-2-(phenylseleno)-2-phenylethylamines by reaction with t-BuLi and subsequent methanolysis of the generated sulfinamide derivatives with TFA.
• Synthesis of Highly Functionalized Pyrrolidines via a Selective Iodide-Mediated Ring Expansion of Methylenecyclopropyl Amides
  作者：Mark E. Scott、Mark Lautens

  DOI：10.1021/jo802049u

  日期：2008.11.7

  iodide-mediated, tandem Mannich/cyclization to afford trans-2,3-disubstituted pyrrolidines from methylenecyclopropyl amides in good to excellent yields and selectivities. The reaction scope has been drastically expanded to include a wide array of aromatic, heteroaromatic and alpha,beta-unsaturated imines, as well as a variety of methylenecyclopropyl amides. Additionally, mechanistic studies were carried out

  该手稿描述了一种高度选择性的碘化物介导的串联曼尼希/环化反应，可从亚甲基环丙基酰胺获得反式-2,3-二取代的吡咯烷，并具有良好的产率和选择性。反应范围已大大扩大，包括各种各样的芳族，杂芳族和α，β-不饱和亚胺，以及各种亚甲基环丙基酰胺。另外，进行了机械研究，以确定使用氘代底物的开环/闭环机理的性质。这些研究的结果表明，其主要机制是S（N）2 / S（N）2开环/闭环，并且碘或碘化物介导的碘烯醇酸酯异构化很可能发生。