(S)-(+)-N-2-thienylidene-p-toluenesulfinamide | 188447-81-6

• 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-2-thienylidene-p-toluenesulfinamide
• 英文别名: (NE,S)-4-methyl-N-(thiophen-2-ylmethylidene)benzenesulfinamide
• CAS: 188447-81-6
• 化学式: C₁₂H₁₁NOS₂
• 分子量: 249.357
• InChiKey: APCTUIACRBPHMQ-WQMJKPAKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  16
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.08
• 拓扑面积：
  76.9
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (S)-(+)-N-2-thienylidene-p-toluenesulfinamide 在 盐酸 、 溶剂黄146 、 naphthalen-1-yl-lithium 作用下， 以 四氢呋喃 、 水 为溶剂， 反应 8.5h， 生成 (R)-N-phthaloyl-1-amino-1-(2-thienyl)methylphosphonic acid
  参考文献：
  名称：

  A new efficient procedure for asymmetric synthesis of α-aminophosphonic acids via addition of lithiated bis(diethylamino)phosphine borane complex to enantiopure sulfinimines

  摘要：

  The addition of lithiated bis(diethylamino)phosphine borane complex to enantiopure p-toluenesulfinimines is highly diastereoselective, affording the corresponding addition products with high efficiency (yields from 72 to 100%). The addition products were readily converted into alpha-amino-alpha-arylmethylphosphonic acids with high enantiomeric purities (from 72 to >98%). (C) 2002 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(02)00684-5
• 作为产物：
  描述：

  2-噻吩甲醛 、 (-)-menthyl p-toluenesulfinate 在 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 为溶剂， 反应 5.0h， 以72%的产率得到(S)-(+)-N-2-thienylidene-p-toluenesulfinamide
  参考文献：
  名称：

  磺胺类药物（硫肟S-氧化物）的不对称合成和性质。

  摘要：

  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。

  DOI：

  10.1021/jo970077e

文献信息

• Diastereoselective addition of diethyl difluoromethylphosphonate to enantiopure sulfinimines: synthesis of α,α-difluoro-β-aminophosphonates, phosphonic acids, and phosphonamidic acids
  作者：Gerd-Volker Röschenthaler、Valery P. Kukhar、Michael Yu. Belik、Kateryna I. Mazurenko、Alexander E. Sorochinsky

  DOI：10.1016/j.tet.2006.08.017

  日期：2006.10

  of diastereomerically pure N-sulfinyl α,α-difluoro-β-aminophosphonates with trifluoroacetic acid in EtOH followed by refluxing with 10 N HCl provided enantiopure α,α-difluoro-β-aminophosphonates and α,α-difluoro-β-aminophosphonic acids. The N-Cbz derivative of (R)-2-amino-1,1-difluoro-2-phenylethylphosphonate was a convenient starting point for the preparation of corresponding difluorophosphonate monoester

  将二乙基硫代二氟甲基膦酸酯加到对映体纯的芳族，杂芳族和脂族醛衍生的亚磺酸亚胺中，得到的N-亚磺酰基α，α-二氟-β-氨基膦酸酯通常具有良好的对映选择性，并且产率很高。与苯乙酮衍生的亚磺胺的反应导致形成具有高非对映选择性且仅中等收率的加成产物。两步脱保护，包括在EtOH中用三氟乙酸处理非对映体纯的N-亚磺酰基α，α-二氟-β-氨基膦酸酯，然后与10 N HCl回流，得到对映体纯的α，α-二氟-β-氨基膦酸酯和α，α-二氟-β-氨基膦酸。（R的N -Cbz导数）-2-氨基-1，1-二氟-2-苯基乙基膦酸酯是制备相应的二氟膦酸酯单酯，二氟膦酸和二氟膦酰胺酸的方便起点。在21°C下，二氟膦酰胺酸在pH高于5的水溶液中稳定。
• A highly efficient asymmetric synthesis of β-aminophosphonic acids, via addition of α-phosphonate carbanions to chiral, enantiopure sulfinimines
  作者：Marian Mikołajczyk、Piotr Łyżwa、Józef Drabowicz、Michał W. Wieczorek、Jarosław Błaszczyk

  DOI：10.1039/cc9960001503

  日期：——

  Addition of alpha-phosphonate carbanions to (S)-sulfinimines 1 affords N-sulfinyl beta-aminophosphonates 2 in a diastereoisomeric ratio from 5:1 to 10:1; the major diastereoisomers of 2, after separation, are converted to the corresponding beta-aminophosphonates 3 or to (+)-beta-amino-beta-phenylethane phosphonic acid 4, whose absolute configuration was established as (R) by X-ray crystallography.
• Ytterbium(III) triflate-catalyzed asymmetric nucleophilic addition of functionalized lithium (α-carbalkoxyvinyl)cuprates to chiral p-toluenesulfinimines (thiooxime S-oxides)
  作者：Guigen Li、Han-Xun Wei、Jason D. Hook

  DOI：10.1016/s0040-4039(99)00756-x

  日期：1999.6

  Ytterbium(III) triflate has been found to catalyze anionic additions of functionalized lithium (alpha-carbalkoxyvinyl)cuprates to chiral p-toluenesulfinimines (thiooxime S-oxides) in a cosolvent system (Et2O-CH2Cl2). This new system has made it possible to utilize those p-toluenesulfinimines of low solubility in Et2O as the electrophiles to react with anionic (alpha-carbalkoxyvinyl)cuprates for the asymmetric synthesis of the corresponding beta-mono and beta,beta-disubstituted Baylis-Hillman adducts. Modest yields (51.0-64.4% yield) and good to excellent diastereoselectivities (>90% de) were obtained. (C) 1999 Elsevier Science Ltd. All rights reserved.
• Asymmetric synthesis of α,α-difluoro-β-amino phosphonic acids using sulfinimines
  作者：Gerd-Volker Röschenthaler、Valery Kukhar、Jan Barten、Natalia Gvozdovska、Michael Belik、Alexander Sorochinsky

  DOI：10.1016/j.tetlet.2004.06.126

  日期：2004.8

  Addition of diethyl lithiodifluoromethylphosphonate to enantiopure sulfinimines afforded the corresponding N-sulfinyl alpha,alpha-diffuoro-beta-amino phosphonates with good diastercoselectivity. A two-step deprotection involving treatment of diastereomerically pure N-sulfinyl alpha,alpha-difluoro-beta-amino phosphonates with trifluoroacetic acid in EtOH followed by refluxing with ION HCl afforded enantiopure alpha,alpha-diffuoro-beta-amino phosphonic acids. (C) 2004 Elsevier Ltd. All rights reserved.
• Asymmetric synthesis of β-monosubstituted and β,β-disubstituted N-(p-toluenesulfinyl)-α-(aminoalkyl)acrylates via anionic additions of (α-carbalkoxyvinyl)cuprates to thiooxime S-oxides
  作者：Han-Xun Wei、Jason D Hook、Keith A Fitzgerald、Guigen Li

  DOI：10.1016/s0957-4166(99)00036-1

  日期：1999.2

  A series of new Baylis-Hillman adducts, beta-monosubstituted and beta,beta-disubstituted N-(p-toluenesulfinyl)-alpha-(aminoalkyl)acrylates has been synthesized via asymmetric nucleophilic additions of (alpha-carbalkoxyvinyl)cuprates to chiral p-toluenesulfinimines. Modest to good yields (52.0-72.0%) and excellent diastereoselectivity (>90% de) have been obtained. The Z/E selectivity was found to be effected by solvents or cosolvents. (C) 1999 Elsevier Science Ltd. All rights reserved.