[(E)-1-Difluoromethyl-2-((R)-toluene-4-sulfinyl)-vinyl]-carbamic acid benzyl ester | 169137-97-7

• 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: [(E)-1-Difluoromethyl-2-((R)-toluene-4-sulfinyl)-vinyl]-carbamic acid benzyl ester
• CAS: 169137-97-7
• 化学式: C₁₈H₁₇F₂NO₃S
• 分子量: 365.401
• InChiKey: KHCWWATYVOCELR-IMYWFDTISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.14
• 重原子数：
  25.0
• 可旋转键数：
  6.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  55.4
• 氢给体数：
  1.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  [(E)-1-Difluoromethyl-2-((R)-toluene-4-sulfinyl)-vinyl]-carbamic acid benzyl ester 在 氢氧化钾 作用下， 以 四氢呋喃 、 甲醇 、 水 为溶剂， 反应 96.0h， 生成 (5R)-5-(difluoromethyl)-5-[[(R)-(4-methylphenyl)sulfinyl]methyl]imidazolidine-2,4-dione
  参考文献：
  名称：

  Enantiomerically pure α-fluoroalkyl-α-amino acids: Synthesis of (R)-α-difluoromethyl-alanine and (S)-α-difluoromethyl-serine

  摘要：

  Hydrocyanation of enantiomerically pure N-Cbz alpha-fluoroalkyl beta-sulfinylenamines 1 occurs smoothly by treatment with KCN or by addition of trimethylsilylcyanide or diethyl phosphorocyanidate to preformed sodium derivatives of 1. The diastereoisomeric difluoro alpha-aminonitriles 2b have been transformed in the unnatural amino acids (R)-alpha-difluoromethyl-alanine and (S)-alpha-difluoromethyl-serine. Copyright (C) 1996 Elsevier Science Ltd

  DOI：

  10.1016/0957-4166(96)00287-x
• 作为产物：
  描述：

  benzyl N-[(Z)-3,3-difluoro-1-[(R)-(4-methylphenyl)sulfinyl]prop-1-en-2-yl]carbamate 以 苯 为溶剂， 生成 [(E)-1-Difluoromethyl-2-((R)-toluene-4-sulfinyl)-vinyl]-carbamic acid benzyl ester
  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。