(S)-(-)-N-<(p-methylthio)benzylidene>-p-toluenesulfinamide | 160751-25-7

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: (S)-(-)-N-<(p-methylthio)benzylidene>-p-toluenesulfinamide
• 英文别名: (S_S)-(-)-N-(p-methylthiobenzylidene)-p-toluenesulfinamide；(S)-(-)-N-(p-(methylthio)benzylidene)-p-toluenesulfinamide；(S)-(-)-N-(4-methylthiobenzylidene)-p-toluenesulfinimine；(NE,S)-4-methyl-N-[(4-methylsulfanylphenyl)methylidene]benzenesulfinamide
• CAS: 160751-25-7
• 化学式: C₁₅H₁₅NOS₂
• 分子量: 289.422
• InChiKey: ZIKDXBBQIZMRGS-SKTWIKFTSA-N

物化性质

• 熔点：
  130-132 °C
• 沸点：
  467.0±55.0 °C(Predicted)
• 密度：
  1.18±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  19
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.13
• 拓扑面积：
  73.9
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (S)-(-)-N-<(p-methylthio)benzylidene>-p-toluenesulfinamide 在 lithium aluminium tetrahydride 、 对甲苯磺酸 、 三乙胺 、 间氯过氧苯甲酸 作用下， 以 四氢呋喃 、 乙醚 、 水 为溶剂， 反应 1.5h， 生成 甲砜霉素
  参考文献：
  名称：

  使用顺式-N-（对甲苯亚磺酰基）氮丙啶2-羧酸不对称合成抗生素（+）-噻吩酚

  摘要：

  分两步从顺式氮丙啶2-羧酸（2S，3S）-制备了广谱抗生素噻吩酚/氟苯尼考的​​前体氨基丙二醇（1R，2R）-（-）- 3的简明高效的不对称合成（-）- 5。

  DOI：

  10.1016/s0040-4039(00)78334-1
• 作为产物：
  描述：

  4-(甲基巯基)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41%的产率得到(S)-(-)-N-<(p-methylthio)benzylidene>-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 Synthesis and Properties of Sulfinimines (Thiooxime <i>S</i>-Oxides)
  作者：Franklin A. Davis、Rajarathnam E. Reddy、Joanna M. Szewczyk、G. Venkat Reddy、Padma S. Portonovo、Huiming Zhang、Dean Fanelli、R. Thimma Reddy,、Ping Zhou、Patrick J. Carroll

  DOI：10.1021/jo970077e

  日期：1997.4.1

  Enantiomerically pure sulfinimines (thiooxime S-oxides 10), important building blocks in the asymmetric synthesis of amine derivatives, are prepared in good to excellent yields in one step from aromatic, heteroaromatic, and aliphatic aldehydes. This protocol involves treating commercially available (R)- or (S)-menthyl p-toluenesufinate (Andersen reagent 4) with LiHMDS, followed by the aldehyde, affording

  对映体纯的亚砜亚胺（硫肟肟S-氧化物10），是胺衍生物不对称合成的重要组成部分，一步一步从芳族，杂芳族和脂族醛制备，收率良好至优异。该方案涉及先用LiHMDS处理醛对苯甲酸酯的（R）-或（S）-薄荷基对甲苯磺酸酯（Andersen试剂4），然后用醛处理，仅得到（E）-10。亚磺胺10是通过甲硅烷基亚磺酰胺阴离子13与醛的Peterson型烯化反应形成的。通过四氧化三锂（12a）与双（三甲基甲硅烷基）亚磺酰胺11的反应生成阴离子13，双（三甲基甲硅烷基）亚磺酰胺11在4与LiHMDS的反应中形成。形成的另一产物是O-（三甲基甲硅烷基）薄荷醇（12c），将其以> 80％的产率分离出来以进行再循环。
• Aza-Darzens Asymmetric Synthesis of <i>N</i>-(<i>p</i>-Toluenesulfinyl)aziridine 2-Carboxylate Esters from Sulfinimines (<i>N</i>-Sulfinyl Imines)
  作者：Franklin A. Davis、Hu Liu、Ping Zhou、Tianan Fang、G. Venkat Reddy、Yulian Zhang

  DOI：10.1021/jo990907j

  日期：1999.10.1

  The one-step aza-Darzens reaction of sulfinimines 2 with lithium alpha-bromoenolates readily affords diversely substituted cis and trans N-sulfinylaziridine 2-carboxylate esters 3 and 7 in good yield and excellent diastereoselectivity. Higher yields, but lower de's, result when a mixture of the alpha-bromo ester and 2 are treated with base. The N-sulfinyl group is transformed, nearly quantitatively, without ring opening, into the N-tosyl activating group by oxidation with m-CPBA. Selective removal of the N-sulfinyl group in aziridines 3a and 3h with TFA/H2O affords VI-aziridines 21 which are difficult to prepared by other means. However, C(3) activated azirines such as 3b undergo ring-opening under these conditions. Alternatively, the N-sulfinyl group, even in C(3)-activated aziridines, was selectively and efficiently removed by treatment of the aziridine with 2 equiv of MeMgBr.
• Synthesis of Enantiopure Sulfinimines (Thiooxime <i>S</i>-Oxides) Catalyzed by Yb(OTf)₃ from <i>p</i>-Toluenesulfinamide and Aldehydes in Mild Reaction Conditions
  作者：Zhi-Yong Jiang、W. H. Chan、A. W. M. Lee

  DOI：10.1021/jo048597e

  日期：2005.2.1

  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.
• Asymmetric synthesis of the antibiotic (+)-thiamphenicol using cis-N-(p-toluenesulfinyl)aziridine 2-carboxylic acids
  作者：Franklin A Davis、Ping Zhou

  DOI：10.1016/s0040-4039(00)78334-1

  日期：1994.10

  A concise, highly efficient asymmetric synthesis of aminopropanediol (1R,2R)-(−)-3, precursor to the broad spectrum antibiotics thiamphenicol/florfenicol , was prepared in two steps from cis-aziridine 2-carboxylic acid (2S,3S)-(−)-5.

  分两步从顺式氮丙啶2-羧酸（2S，3S）-制备了广谱抗生素噻吩酚/氟苯尼考的​​前体氨基丙二醇（1R，2R）-（-）- 3的简明高效的不对称合成（-）- 5。