(R)-(-)-1-(4-nitrophenyl)-1,2-ethanediol | 77977-74-3

• 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: (R)-(-)-1-(4-nitrophenyl)-1,2-ethanediol
• 英文别名: (R)-1-(4-nitrophenyl)ethane-1,2-diol；(R)-p-nitrophenylethane-1,2-diol；(R)-p-nitrophenyl glycol；(1R)-1-(4-nitrophenyl)ethane-1,2-diol
• CAS: 77977-74-3
• 化学式: C₈H₉NO₄
• mdl: MFCD02667811
• 分子量: 183.164
• InChiKey: YOJHBFHEOQUUAR-QMMMGPOBSA-N

物化性质

• 沸点：
  398.7±32.0 °C(Predicted)
• 密度：
  1.410±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.2
• 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：
  86.3
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (R)-(-)-1-(4-nitrophenyl)-1,2-ethanediol 在 氢溴酸 作用下， 以 乙醇 为溶剂， 反应 25.0h， 生成 (-)-硝苯洛尔
  参考文献：
  名称：

  Preparing β-blocker (R)-Nifenalol based on enantioconvergent synthesis of (R)-p-nitrophenylglycols in continuous packed bed reactor with epoxide hydrolase

  摘要：

  An engineered epoxide hydrolase from Vigna radiate (VrEH2(M263N)) shows near-perfect enantioconvergence in single enzyme mediated hydrolysis of racemic p-nitrostyrene oxide (pNSO). To explore industrial potential of the promising biocatalyst, we tried to immobilize the VrEH2 variant by covalently linking onto a commercially available amino resin ECR8405F. Then a 5-mL packed bed reactor filled with the immobilized VrEH2(M263N) was connected with macroporous resin NKA-11 for in situ product adsorption, and the product (R)-p-nitrophenyl glycol (pNPG) was harvested by methanol elution, with 91% isolated yield and 97% ee. The continuous reactor was operated stably for more than 100 h with a space time yield of 20 g.L-1.h(-1). Subsequently, the beta-blocker (R)-Nifenalol was prepared by chemically synthesized from (R)-pNPG, affording the product in an overall yield of 61.3% (1.5 g) and an enantiopurity of 99.9% ee after recrystallization. (C) 2019 Published by Elsevier Ltd.

  DOI：

  10.1016/j.tet.2019.01.034
• 作为产物：
  描述：

  4-硝基苯乙烯 在 potassium osmate(VI) 、 mono-quinidine derivative of (S)-(3-pyridazinyl)-t-butyl-1-anthracenylmethyl) ether (1 molpercent) 、 potassium carbonate 、 potassium hexacyanoferrate(III) 作用下， 以 水 、 叔丁醇 为溶剂， 生成 (R)-(-)-1-(4-nitrophenyl)-1,2-ethanediol
  参考文献：
  名称：

  机械设计的单金鸡纳生物碱是烯烃对映选择性二羟基化的极佳催化剂

  摘要：

  根据最近提出的关于OsO 4促进的由双金鸡纳生物碱衍生物（例如1）催化的烯烃的二羟基化中对映选择性的起源的想法，特别是有强有力的证据证明通过过渡态组装体2可以进行反应，单奎尼丁衍生物3是被选为有前途的催化配体。由3促进的高对映选择性的实验观察提供了有利于过渡态2的其他证据。

  DOI：

  10.1016/s0040-4039(00)78237-2

文献信息

• A mechanistically designed mono-cinchona alkaloid is an excellent catalyst for the enantioselective dihydroxylation of olefins
  作者：E.J. Corey、Mark C. Noe、Michael J. Grogan

  DOI：10.1016/s0040-4039(00)78237-2

  日期：1994.8

  advanced regarding the origin of enantioselectivity in the OsO4-promoted dihydroxylation of olefins catalyzed by bis-cinchona alkaloid derivatives such as 1, specifically strong evidence for reaction via transition state assembly 2, the mono-quinidine derivative 3 was selected as a promising catalytic ligand. The experimental observation of high enantioselectivity promoted by 3 provides additional

  根据最近提出的关于OsO 4促进的由双金鸡纳生物碱衍生物（例如1）催化的烯烃的二羟基化中对映选择性的起源的想法，特别是有强有力的证据证明通过过渡态组装体2可以进行反应，单奎尼丁衍生物3是被选为有前途的催化配体。由3促进的高对映选择性的实验观察提供了有利于过渡态2的其他证据。
• Microbiological Transformations. 33. Fungal Epoxide Hydrolases Applied to the Synthesis of Enantiopure <i>Para</i>-Substituted Styrene Oxides. A Mechanistic Approach
  作者：S. Pedragosa-Moreau、C. Morisseau、J. Zylber、A. Archelas、J. Baratti、R. Furstoss

  DOI：10.1021/jo960558i

  日期：1996.1.1

  para-substituted styrene oxide derivatives was studied, using whole cells of the fungi Aspergillus niger or Beauveria sulfurescens. These microorganisms proved to be equipped with epoxide hydrolases which are able to achieve these hydrolyses with high enantioselectivity. This allowed the preparation of the optically active epoxides and of the corresponding vicinal diols which were obtained with good to excellent

  使用黑曲霉或白僵菌的全细胞研究了不同对位取代的氧化苯乙烯衍生物的生物水解。这些微生物被证明配备有环氧化物水解酶，其能够以高对映选择性实现这些水解。这样就可以制备旋光性环氧化物和相应的邻位二醇，它们的对映体纯度很好。这两种微生物被证明是对映体互补的。使用来自黑曲霉的粗冻干酶提取物进行的机理研究通过哈米特系数图表明该水解很可能是由于一般的碱催化过程。
• Manipulating regioselectivity of an epoxide hydrolase for single enzymatic synthesis of (<i>R</i>)-1,2-diols from racemic epoxides
  作者：Die Hu、Xun-Cheng Zong、Feng Xue、Chuang Li、Bo-Chun Hu、Min-Chen Wu

  DOI：10.1039/d0cc00283f

  日期：——

  Both the activity and regioselectivity of Phaseolus vulgaris epoxide hydrolase were remarkably improved via reshaping two substrate tunnels based on rational design. The elegant one-step enantioconvergent hydrolysis of seven rac-epoxides was achieved by single mutants, allowing green and efficient access to valuable (R)-1,2 diols with high eep (90.1-98.3%) and yields.

  通过合理设计重整两个底物通道，可显着提高菜豆环氧化物水解酶的活性和区域选择性。通过单一突变体实现了七个rac环氧的优雅的一步对映体聚合水解，可绿色高效地获得有价值的（R）-1,2二醇，具有高碱（90.1-98.3％）和产率。
• Highly regio- and enantio-selective hydrolysis of two racemic epoxides by GmEH3, a novel epoxide hydrolase from Glycine max
  作者：Chen Zhang、Chuang Li、Xiu-xiu Zhu、You-yi Liu、Jun Zhao、Min-chen Wu

  DOI：10.1016/j.ijbiomac.2020.08.011

  日期：2020.12

  50 mM−1 s−1) of purified GmEH3 for (S)-5a was slightly higher than that (kcatR/KmR = 1.52 mM−1 s−1) for (R)-5a, whereas the kcat/Km (5.16 mM−1 s−1) for (S)-7a was much higher than that (0.09 mM−1 s−1) for (R)-7a. Using 200 mg/mL wet cells of E. coli/gmeh3 as the biocatalyst, the scale-up enantioconvergent hydrolysis of 150 mM rac-5a at 25 °C for 1.5 h afforded (R)-5b with 90.2% eep and 95.4% yieldp

  基于计算机辅助分析，从大豆中挖掘出一种新型环氧化物水解酶，命名为Gm EH3。然后，克隆了Gm EH3编码基因gmeh3 ，并在大肠杆菌Rosetta(DE3)中成功表达。在所研究的十种外消旋环氧化物中， Gm EH3 在外消旋间氯苯乙烯氧化物 ( 5a ) 的不对称水解中具有最高和最好的互补区域选择性（区域选择性系数， α S = 93.7% 和 β R = 97.2%），并且对外消旋苯基缩水甘油醚 ( 7a ) 具有最高的对映选择性（对映体比率， E = 55.6）。纯化的Gm EH3 对 ( S )- 5a的催化效率 ( k cat S / K m S = 2.50 mM -1 s -1 ) 略高于 ( k cat R / K m R = 1.52 mM -1 s - ) 1 ) ( R )- 5a ，而 ( S )- 7a的k cat / K m (5.16 mM −1 s −1 )
• Converting an Esterase into an Epoxide Hydrolase
  作者：Helge Jochens、Konstanze Stiba、Christopher Savile、Ryota Fujii、Juin-Guo Yu、Tatsiana Gerassenkov、Romas J. Kazlauskas、Uwe T. Bornscheuer

  DOI：10.1002/anie.200806276

  日期：2009.4.27

  Entering the fold: A common structural motif in hydrolytic enzymes is the α,β‐hydrolase fold. The interconversion of one enzyme into another by introduction of mechanistically important residues is not enough; only substitution of a loop allows epoxide hydrolase activity in the esterase scaffold to be formed (see picture; structure comparison of epoxide hydrolases (green) with the esterase (orange))

  进入折叠：水解酶的常见结构基序是α，β-水解酶折叠。通过引入具有机械重要性的残基将一种酶相互转化为另一种酶是不够的。仅环的取代允许在酯酶支架中形成环氧化物水解酶活性（参见图片；环氧化物水解酶（绿色）与酯酶（橙色）的结构比较）。结果是对映选择性嵌合酶。