(S)-2-fluoro-1-(4-nitrophenyl)ethanol

• 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)-2-fluoro-1-(4-nitrophenyl)ethanol
• 英文别名: (1S)-2-Fluoro-1-(4-nitrophenyl)ethan-1-ol；(1S)-2-fluoro-1-(4-nitrophenyl)ethanol
• 化学式: C₈H₈FNO₃
• 分子量: 185.155
• InChiKey: ALYBAZKHBOZEHB-MRVPVSSYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  13
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  66
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  2-fluoro-1-(4-nitrophenyl)ethanone 在 Lactobacillus brevis alcohol dehydrogenase 、 烟酰胺腺嘌呤双核苷酸磷酸盐 、 magnesium chloride 作用下， 以 异丙醇 为溶剂， 反应 24.0h， 以95%的产率得到(S)-2-fluoro-1-(4-nitrophenyl)ethanol
  参考文献：
  名称：

  Synthesis of Enantiopure Fluorohydrins Using Alcohol Dehydrogenases at High Substrate Concentrations

  摘要：

  The use of purified and overexpressed alcohol dehydrogenases to synthesize enantiopure fluorinated alcohols is shown. When the bioreductions were performed with ADH-A from Rhodococcus ruber overexpressed in E. coli, no external cofactor was necessary to obtain the enantiopure (R)-derivatives. Employing Lactobacillus brevis ADH, it was possible to achieve the synthesis of enantiopure (S)-fluorohydrins at a 0.5 M substrate concentration. Furthermore, due to the activated character of these substrates, a huge excess of the hydrogen donor was not necessary.

  DOI：

  10.1021/jo400962c

文献信息

• Enantioenriched 1-aryl-2-fluoroethylamines. Efficient lipase-catalysed resolution and limitations to the Mitsunobu inversion protocol
  作者：Thor Håkon Krane Thvedt、Erik Fuglseth、Eirik Sundby、Bård Helge Hoff

  DOI：10.1016/j.tet.2010.06.081

  日期：2010.8

  inversion protocol starting with enantioenriched 1-aryl-2-fluoroethanols using phthalimide as nucleophile was employed in the synthesis of the (S)-1-aryl-2-fluoroethylamines. Both the inversion efficiency and yield depended on the aromatic substituents. For six of the substrates, clean inversion of the stereochemistry was observed. However, racemisation and low yields were the result when electron-donating

  八个1-芳基-2-氟乙胺的两种对映体均以1-芳基-2-氟乙酮为原料合成。使用南极假丝酵母的脂肪酶B和甲氧基乙酸乙酯作为酰基供体对胺进行动力学拆分，得到96.99％ee的（R）-胺和> 99.5％ee的（S）-甲氧基乙酰胺。关于反应温度，酰基给体浓度，水活度和底物结构的变化，分离度很强。其他九种脂肪酶制剂未能催化该反应或对映选择性低。其次，在合成（（S）时，采用以苯二甲酰亚胺为亲核试剂的对映体富集的1-芳基-2-氟乙醇为原料的Mitsunobu转化方案。）-1-芳基-2-氟乙胺。转化效率和产率均取决于芳族取代基。对于六种底物，观察到立体化学的完全反转。但是，当芳族环上存在供电子性取代基时，外消旋化和低收率是结果。当用氰基或硝基取代时，会发生意想不到的氟消除，从而限制了这些转化的收率。使用圆二色性确定1-芳基-2-氟乙胺的绝对构型。
• Asymmetric reduction using (R)-MeCBS and determination of absolute configuration of para-substituted 2-fluoroarylethanols
  作者：Erik Fuglseth、Eirik Sundby、Per Bruheim、Bård Helge Hoff

  DOI：10.1016/j.tetasy.2008.07.019

  日期：2008.8

  The asymmetric reduction of eight alpha-fluoroacetophenones has been investigated using (R)-MeCBS as a catalyst in various media. Based on a solvent screen, 1,2-dimethoxyethane, diethyl ether and dichloromethane were used in reductions of the alpha-fluoroacetophenones. The enantiomeric excess of the products depended oil the solvent and the electronic character of the aromatic substituents. Higher enantioselectivity and less solvent dependency were observed in the reduction of substrates bearing electron donating substituents, whereas the opposite was the case for reduction of the substrates with electron withdrawing substituents. The (R)-2-fluoro-1-arylethanols were obtained with enantiomeric excesses in the range of 91-99% using 1,2-dimethoxyethane as a solvent. Six of the alcohols produced are new chemical entities. The absolute configurations of the (R)-2-fluoro-1-arylethanols were determined by circular dichroism using the exciton chirality method of tile (S)-benzoate esters of the alcohols. The (S)-benzoate esters were obtained by lipase-catalysed resolution using Novozym 435. (C) 2008 Elsevier Ltd. All Fights reserved.
• Ruthenium-catalysed asymmetric transfer hydrogenation of para-substituted α-fluoroacetophenones
  作者：Erik Fuglseth、Eirik Sundby、Bård H. Hoff

  DOI：10.1016/j.jfluchem.2009.03.011

  日期：2009.6

  The first examples of asymmetric transfer hydrogenation of alpha-fluoroacetophenones are reported. Eight para-substituted a-fluoroacetophenones have been reduced using four catalytic systems constructed of [RuCl2(p-cymene)(2)](2) or [RuCl2(mesitylene)(2)](2) in combinations with each of the ligands (1R,2R)-N-(p-toluenesulfonyl)-1,2-diphenylethylenediamine ((R,R)-TsDPEN) and (1R,2R)-N-(p-toluenesulfonyl)-1,2cyclohexanediamine ((R,R)-TsCYDN). All reactions were performed in both water and formic acid/triethylamine. The highest enantioselectivity was obtained using the (R,R)-TsDPEN ligand in a formic acid/triethylamine mixture, giving the (S)-1-aryl-2-fluoroethanols in high to moderate enantiomeric excess (97.5-84.5%). For this solvent system the presence of electron withdrawing groups in the para position reduced the enantioselectivity. Reactions performed in water generally gave lower enantioselectivity and reaction rate, although RuCl(mesitylene)-(R,R)-TsDPEN yielded the product alcohols with enantiomeric excess in the range of 95.5-76.5%. (c) 2009 Elsevier B.V. All rights reserved.
• Synthesis of Enantiopure Fluorohydrins Using Alcohol Dehydrogenases at High Substrate Concentrations
  作者：Wioleta Borzęcka、Iván Lavandera、Vicente Gotor

  DOI：10.1021/jo400962c

  日期：2013.7.19

  The use of purified and overexpressed alcohol dehydrogenases to synthesize enantiopure fluorinated alcohols is shown. When the bioreductions were performed with ADH-A from Rhodococcus ruber overexpressed in E. coli, no external cofactor was necessary to obtain the enantiopure (R)-derivatives. Employing Lactobacillus brevis ADH, it was possible to achieve the synthesis of enantiopure (S)-fluorohydrins at a 0.5 M substrate concentration. Furthermore, due to the activated character of these substrates, a huge excess of the hydrogen donor was not necessary.