(Z)-3,3,3-trifluoro-1-[(R)-(4-methylphenyl)sulfinyl]prop-1-en-2-amine | 169137-94-4

• 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: (Z)-3,3,3-trifluoro-1-[(R)-(4-methylphenyl)sulfinyl]prop-1-en-2-amine
• CAS: 169137-94-4
• 化学式: C₁₀H₁₀F₃NOS
• 分子量: 249.257
• InChiKey: YCTCEPJQRIQFCJ-CXOKCQFOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  16
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  62.3
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  (Z)-3,3,3-trifluoro-1-[(R)-(4-methylphenyl)sulfinyl]prop-1-en-2-amine 在 sodium tetrahydroborate 、 potassium carbonate 作用下， 以 四氢呋喃 、 1,4-二氧六环 、 水 为溶剂， 反应 3.0h， 生成 benzyl N-[(2S)-1,1,1-trifluoro-3-[(R)-(4-methylphenyl)sulfinyl]propan-2-yl]carbamate
  参考文献：
  名称：

  New Versatile Fluorinated Chiral Building Blocks:  Synthesis and Reactivity of Optically Pure α-(Fluoroalkyl)-β-sulfinylenamines

  摘要：

  Efficient synthesis of optically pure alpha-(fluoroalkyl)-beta-sulfinyl enamines has been achieved by aza-Wittig reaction of triphenyliminophosphoranes with the corresponding alpha-fluorinated-alpha'-sulfinyl ketones. The title compounds 3,4 showed an overwhelming preference for the Z stereochemistry of the enamine form. Their general reactivity has been studied. The reaction with some electrophiles (i.e. benzyl chloroformate and benzyl and allyl bromide) occurs at the nitrogen atom providing the corresponding N,N-disubstituted enamines. Nucleophiles add smoothly to C-2: heteroatom-centered nucleophiles like methanol, ammonia, and thiophenol afford gem-disubstituted derivatives under thermodynamic control, while a C-centered nucleophile like nitromethane adds in irreversible fashion. The hydride- and deuteride-promoted reduction of 3,4 to the N-Cbz-protected (14) and N-unprotected (15) alpha-fluorinated-alpha'-sulfinyl amines has been studied. Hydride addition was stereoselective, while low stereoselection was obtained with the other tested nucleophiles. Desulfurization of the optically pure 1,1,1-trifluoro-3-sulfinyl amine 15a afforded (R)-1-(trifluoromethyl)ethylamine 17. The Pummerer rearrangement of 14 occurs in an unusual nonoxidative way affording the sulfenamide 24, that readily provided (R)-(2-H)- and -(2-D)-3,3,3-trifluoroalaninol (19) and (R)-3,3,3-trifluoroalanine (22).

  DOI：

  10.1021/jo952097r
• 作为产物：
  描述：

  1,1,1-三甲基-N-(三苯基正膦亚基)硅烷胺 、 1,1,1-trifluoro-3-[(R)-(4-methylphenyl)sulfinyl]propan-2-one 以 甲苯 、 苯 为溶剂， 反应 14.0h， 以91%的产率得到(Z)-3,3,3-trifluoro-1-[(R)-(4-methylphenyl)sulfinyl]prop-1-en-2-amine
  参考文献：
  名称：

  New Versatile Fluorinated Chiral Building Blocks:  Synthesis and Reactivity of Optically Pure α-(Fluoroalkyl)-β-sulfinylenamines

  摘要：

  Efficient synthesis of optically pure alpha-(fluoroalkyl)-beta-sulfinyl enamines has been achieved by aza-Wittig reaction of triphenyliminophosphoranes with the corresponding alpha-fluorinated-alpha'-sulfinyl ketones. The title compounds 3,4 showed an overwhelming preference for the Z stereochemistry of the enamine form. Their general reactivity has been studied. The reaction with some electrophiles (i.e. benzyl chloroformate and benzyl and allyl bromide) occurs at the nitrogen atom providing the corresponding N,N-disubstituted enamines. Nucleophiles add smoothly to C-2: heteroatom-centered nucleophiles like methanol, ammonia, and thiophenol afford gem-disubstituted derivatives under thermodynamic control, while a C-centered nucleophile like nitromethane adds in irreversible fashion. The hydride- and deuteride-promoted reduction of 3,4 to the N-Cbz-protected (14) and N-unprotected (15) alpha-fluorinated-alpha'-sulfinyl amines has been studied. Hydride addition was stereoselective, while low stereoselection was obtained with the other tested nucleophiles. Desulfurization of the optically pure 1,1,1-trifluoro-3-sulfinyl amine 15a afforded (R)-1-(trifluoromethyl)ethylamine 17. The Pummerer rearrangement of 14 occurs in an unusual nonoxidative way affording the sulfenamide 24, that readily provided (R)-(2-H)- and -(2-D)-3,3,3-trifluoroalaninol (19) and (R)-3,3,3-trifluoroalanine (22).

  DOI：

  10.1021/jo952097r

文献信息

• Stereoselective synthesis of optically pure γ-fluoro-β-enaminosulfoxides and reduction to γ-fluoro-β-aminosulfoxides
  作者：Pierfrancesco Bravo、Marcello Crucianelli、Matteo Zanda

  DOI：10.1016/0040-4039(95)00422-9

  日期：1995.4

  The aza-Wittig reaction of phospha-λ5-azenes with optically pure γ-fluorosubstituted β-ketosulfoxides leads to the corresponding β-enaminosulfoxides, which were easily isolated in diastereomerically pure form. The stereoselective reduction of the enamine 3cb afforded the optically pure β-sulphinyl-amine 5cb in high overall yield.

  phospha-的氮杂Wittig反应λ 5 -azenes与光学纯γ-β氟取代的- ketosulfoxides通向相应β-enaminosulfoxides，将其容易地在对映异构纯形式分离。烯胺3cb的立体选择性还原以高的总收率提供了光学纯的β-亚磺酰基胺5cb。
• Unusual non-oxidative pummerer rearrangement of γ-trifluoro-β-aminosulfoxides
  作者：Alberto Arnone、Pierfrancesco Bravo、Luca Bruché、Marcello Crucianelli、Lucia Vichi、Matteo Zanda

  DOI：10.1016/0040-4039(95)01470-3

  日期：1995.10

  Trifluoroacetic anhydride promoted Pummerer rearrangement of γ-trifluoro-β-amino sulfoxides 1 follows an unusual pathway, in which a migration of the p-tolylthio group to the nitrogen atom provides the corresponding α-sulfenamidotrifluoroacetates 5. The usual removal of the proton in α to the sulfinyl moiety does not take place, as shown by maintenance of deuterium during the rearrangement. This procedure is exploited

  三氟乙酸酐促进γ-三氟-β-氨基亚砜1的Pummerer重排遵循一条不寻常的途径，其中对甲苯甲硫基向氮原子的迁移提供了相应的α-亚磺酰胺基三氟乙酸酯5。正如重排过程中维持氘所表明的那样，通常不会发生α中质子向亚磺酰基部分的常规去除。该程序用于2D和2H-（R）-2-氨基-3,3,3-三氟丙烷-1-醇10的立体选择性合成。
• Highly Stereoselective Tandem Pummerer Reaction/α-Hydroxy Imine Rearrangement of E.P. β-Sulfinylenamines
  作者：Pierfrancesco Bravo、Marcello Crucianelli、Alessandro Volonterio、Matteo Zanda

  DOI：10.1080/10426509708545545

  日期：1997.1.1
• New Versatile Fluorinated Chiral Building Blocks:  Synthesis and Reactivity of Optically Pure α-(Fluoroalkyl)-β-sulfinylenamines
  作者：Alberto Arnone、Pierfrancesco Bravo、Silvia Capelli、Giovanni Fronza、Stefano V. Meille、Matteo Zanda、Giancarlo Cavicchio、Marcello Crucianelli

  DOI：10.1021/jo952097r

  日期：1996.1.1

  Efficient synthesis of optically pure alpha-(fluoroalkyl)-beta-sulfinyl enamines has been achieved by aza-Wittig reaction of triphenyliminophosphoranes with the corresponding alpha-fluorinated-alpha'-sulfinyl ketones. The title compounds 3,4 showed an overwhelming preference for the Z stereochemistry of the enamine form. Their general reactivity has been studied. The reaction with some electrophiles (i.e. benzyl chloroformate and benzyl and allyl bromide) occurs at the nitrogen atom providing the corresponding N,N-disubstituted enamines. Nucleophiles add smoothly to C-2: heteroatom-centered nucleophiles like methanol, ammonia, and thiophenol afford gem-disubstituted derivatives under thermodynamic control, while a C-centered nucleophile like nitromethane adds in irreversible fashion. The hydride- and deuteride-promoted reduction of 3,4 to the N-Cbz-protected (14) and N-unprotected (15) alpha-fluorinated-alpha'-sulfinyl amines has been studied. Hydride addition was stereoselective, while low stereoselection was obtained with the other tested nucleophiles. Desulfurization of the optically pure 1,1,1-trifluoro-3-sulfinyl amine 15a afforded (R)-1-(trifluoromethyl)ethylamine 17. The Pummerer rearrangement of 14 occurs in an unusual nonoxidative way affording the sulfenamide 24, that readily provided (R)-(2-H)- and -(2-D)-3,3,3-trifluoroalaninol (19) and (R)-3,3,3-trifluoroalanine (22).