(-)-(2R)-2-(N-benzyloxycarbonyl)amino-3,3,3-trifluoropropanol | 172364-77-1

• 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: (-)-(2R)-2-(N-benzyloxycarbonyl)amino-3,3,3-trifluoropropanol
• 英文别名: N-Cbz-3,3,3-trifluoroalaninol；benzyl N-[(2R)-1,1,1-trifluoro-3-hydroxypropan-2-yl]carbamate
• CAS: 172364-77-1
• 化学式: C₁₁H₁₂F₃NO₃
• 分子量: 263.216
• InChiKey: WJMBSGOEVXOCMI-SECBINFHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  18
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  58.6
• 氢给体数：
  2
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  (-)-(2R)-2-(N-benzyloxycarbonyl)amino-3,3,3-trifluoropropanol 在 ruthenium(IV) oxide 、 sodium periodate 作用下， 以 水 、 丙酮 为溶剂， 反应 1.0h， 以65%的产率得到(-)-(2R)-N-benzyloxycarbonyl-3,3,3-trifluoroalanine
  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：

  benzyl N-[(Z)-3,3,3-trifluoro-1-[(R)-(4-methylphenyl)sulfinyl]prop-1-en-2-yl]carbamate 在 sodium tetrahydroborate 作用下， 以 四氢呋喃 、 水 为溶剂， 反应 3.0h， 生成 (-)-(2R)-2-(N-benzyloxycarbonyl)amino-3,3,3-trifluoropropanol
  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

• 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。
• Asymmetric Synthesis of Fluorinated Amino Macrolactones through Ring-Closing Metathesis
  作者：Santos Fustero、Begoña Fernández、Juan F. Sanz-Cervera、Natalia Mateu、Silvia Mosulén、Rodrigo J. Carbajo、Antonio Pineda-Lucena、Carmen Ramírez de Arellano

  DOI：10.1021/jo701484w

  日期：2007.11.1

  The synthesis of new chiral fluorinated amino and azamacrolactones of types 1 and 2 is described. A ring-closing metathesis (RCM) reaction constitutes the key step in this methodology, which uses fluorinated amino alcohols 7 as starting materials. The influence of the CF2 group, which is located in the (x-position relative to the carbon bearing the amino group, on the efficiency of the RCM reaction is noteworthy. This method allows for the preparation of the desired fluorinated macrolactones in excellent yields.
• Enantioselective Synthesis of Fluorinated α-Amino Acids and Derivatives in Combination with Ring-Closing Metathesis:  Intramolecular π-Stacking Interactions as a Source of Stereocontrol
  作者：Santos Fustero、Antonio Navarro、Belén Pina、Juan García Soler、Ana Bartolomé,、Amparo Asensio、Antonio Simón、Pierfrancesco Bravo、Giovanni Fronza、Alessandro Volonterio、Matteo Zanda

  DOI：10.1021/ol016087q

  日期：2001.8.1

  [GRAPHICS]Hydride reduction of C=N bonds stereocontrolled by intramolecular m-stacking interactions of 1-naphthylsulfinyl and N-aryl groups, nonoxidative Pummerer rearrangement, and ring-closing metathesis are efficiently combined in a highly stereoselective entry to enantiomerically pure cyclic and acyclic fluorinated beta -amino alcohols and alpha -amino acid derivatives, respectively.