(S)-2-(2-Nitrophenylamino)-3-phenyl-propan-1-ol | 1313392-74-3

• 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: (S)-2-(2-Nitrophenylamino)-3-phenyl-propan-1-ol
• 英文别名: (2S)-2-(2-nitroanilino)-3-phenylpropan-1-ol
• CAS: 1313392-74-3
• 化学式: C₁₅H₁₆N₂O₃
• 分子量: 272.304
• InChiKey: LQHYXLCBWUCGSV-ZDUSSCGKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  20
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  78.1
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (S)-2-(2-Nitrophenylamino)-3-phenyl-propan-1-ol 在 palladium 10% on activated carbon 、 氢气 、 三苯基膦 、 偶氮二甲酸二乙酯 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 2.0h， 生成
  参考文献：
  名称：

  Inter- and intramolecular Mitsunobu reaction and metal complexation study: synthesis of S-amino acids derived chiral 1,2,3,4-tetrahydroquinoxaline, benzo-annulated [9]-N3 peraza, [12]-N4 peraza-macrocycles

  摘要：

  合成了替代的1,2,3,4-四氢喹喔啉、苯环附加的不对称手性[9]-N3佩拉扎和[12]-N4佩拉扎大环，采用分子间和分子内的Mitsunobu反应，从氨基酸衍生的共同合成中间体3开始。这些大环的金属配位研究通过紫外-可见光谱技术进行，结合常数（Kb）值为1.84 × 10^3 dm^3 mol−1，使用Benesi–Hildebrand方程，并在35°C下，14天内对于Co2+的吉布斯自由能（ΔG）为-19.4 kJ mol−1。金属的结合特性依赖于聚氮大环的结构，这一点通过DFT优化的两个大环的结构得到确认。详细探讨了大环的紫外-可见光谱及其完整解释，并借助TD-DFT以及前沿分子轨道计算进行了分析。

  DOI：

  10.1039/c1ob06304a
• 作为产物：
  描述：

  (S)-methyl 2-(2-nitrophenylamino)-3-phenylpropanoate 在 锂硼氢 作用下， 以 四氢呋喃 为溶剂， 反应 1.0h， 以85%的产率得到(S)-2-(2-Nitrophenylamino)-3-phenyl-propan-1-ol
  参考文献：
  名称：

  通过重氮-氧键的形成和对映体纯的1-烷基苯并三唑衍生物的合成，史无前例地形成了苯并[ d ] [1,2,3,6]草三唑胺衍生物

  摘要：

  通过氨基酸衍生的苯并稠合的脂环族的重氮化，制备了一系列氨基酸衍生的对映体纯的苯并[ d ] [1,2,3,6]恶三唑胺衍生物和1-烷基取代的苯并三唑。在酸性介质中第一个前所未有的重氮-氧键形成导致了一种全新的取代苯并[ d ] [1,2,3,6]恶三唑嗪杂环。

  DOI：

  10.1016/j.tetlet.2011.04.049

文献信息

• Design of Chiral Hydroxyalkyl‐ and Hydroxyarylazolinium Salts as New Chelating Diaminocarbene Ligand Precursors Devoted to Asymmetric Copper‐Catalyzed Conjugate Addition
  作者：Diane Rix、Stéphane Labat、Loïc Toupet、Christophe Crévisy、Marc Mauduit

  DOI：10.1002/ejic.200801243

  日期：2009.5

  The design and the synthesis of a set of new chiral hydroxyalkyl- and hydroxyaryl-chelating diaminocarbene ligands is reported. Comparative catalytic studies show the importance of the scaffold design around the NHC unit to obtain a high enantiocontrol in Cu-catalyzed asymmetric conjugate addition (ACA). Whereas low selectivities are observed when the stereogenic centre is placed within the N-heterocyclic

  报道了一组新的手性羟烷基和羟芳基螯合二氨基卡宾配体的设计和合成。比较催化研究表明围绕 NHC 单元的支架设计对于在 Cu 催化的不对称共轭加成 (ACA) 中获得高对映控制的重要性。当立体中心位于 N-杂环内时观察到低选择性，当中心手性位于两条侧链内时可以观察到有趣的匹配效应，这使得催化反应中的 ee 达到 92%。 (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)
• Unprecedented formation of benzo[d][1,2,3,6]oxatriazocine derivatives via diazo-oxygen bond formation and synthesis of enantiomerically pure 1-alkyl benzotriazole derivatives
  作者：Saurav Bera、Krishnananda Samanta、Gautam Panda

  DOI：10.1016/j.tetlet.2011.04.049

  日期：2011.6

  A series of amino acid-derived enantiomerically pure substituted benzo[d][1,2,3,6]oxatriazocine derivatives and 1-alkyl substituted benzotriazoles has been prepared by the diazotization of amino acid-derived benzo-fused alicycles. The first unprecedented diazo-oxygen bond formation in acidic medium led to an entirely new kind of substituted benzo[d][1,2,3,6]oxatriazocine heterocycles.

  通过氨基酸衍生的苯并稠合的脂环族的重氮化，制备了一系列氨基酸衍生的对映体纯的苯并[ d ] [1,2,3,6]恶三唑胺衍生物和1-烷基取代的苯并三唑。在酸性介质中第一个前所未有的重氮-氧键形成导致了一种全新的取代苯并[ d ] [1,2,3,6]恶三唑嗪杂环。
• Chiral ethylene-bridged flavinium salts: the stereoselectivity of flavin-10a-hydroperoxide formation and the effect of substitution on the photochemical properties
  作者：Jiří Žurek、Eva Svobodová、Jiří Šturala、Hana Dvořáková、Jiří Svoboda、Radek Cibulka

  DOI：10.1016/j.tetasy.2017.10.029

  日期：2017.12

  A series of chiral non-racemic N-1,N-10-ethylene bridged flavinium salts 4 was prepared using enantiomerically pure 2-substituted 2-aminoethanols (R = isopropyl, phenyl, benzyl, 4-methoxybenzyl, 4-benzyloxybenzyl) derived from amino acids as the sole source of chirality. The flavinium salts were shown to form 10a-hydroperoxy- and 10a-methoxy-adducts with moderate to high diastereoselectivity depending on the ethylene bridge substituent originating from the starting amino acid. High diastereoselectivities (dr values from 80:20 to >95:5) were observed for flavinium salts bearing benzyl substituents attached to the ethylene bridge. The benzyl group preferred the face-to-face (syn) orientation relative to the flavinium unit; thereby effectively preventing nucleophilic attack from one side. This conformation was found to be the most stable according to the DFT calculations. Consequently, the presence of benzyl groups causes intermolecular fluorescence quenching resulting in a significant decrease in the fluorescence quantum yield from 11% for 4a bearing an isopropyl substituent to 0.3% for 4c containing a benzyl group and to a value lower than 0.1% for the benzyloxybenzyl derivative 4e. (C) 2017 Elsevier Ltd. All rights reserved.
• Asymmetric Hydrogenation of Quinoxalines, Benzoxazines, and a Benzothiazine Catalyzed by Chiral Ruthenabicyclic Complexes
  作者：Noriyoshi Arai、Yu Saruwatari、Kotaro Isobe、Takeshi Ohkuma

  DOI：10.1002/adsc.201300604

  日期：2013.10.11

  AbstractThe ruthenabicyclic complex RuCl[(R)‐daipena][(R)‐dm‐segphos] with potassium tert‐butoxide catalyzes the hydrogenation of 2‐alkylquinoxalines and a 3‐methyl‐2H‐1,4‐benzoxazine in toluene under 20–100 atm of hydrogen at 40 °C to afford S‐configured cyclic amino products in greater than 97% enantiomeric excess DAIPENA=anion of DAIPEN at the 2‐position of an anisyl group, DAIPEN=1,1‐di(4‐anisyl)‐2‐isopropyl‐1,2‐ethylenediamine, DM‐SEGPHOS=(4,4′‐bi‐1,3‐benzodioxole)‐5,5′‐diylbis[di(3,5‐xylyl)phosphine]}. The high catalytic activity results in a turnover number as high as 9400. Hydrogenation of the benzoimine heterocycles with the RuCl[(R)‐daipena][(R)‐segphos]/potassium tert‐butoxide system yields the R‐configured products in high enantiomeric excess [SEGPHOS=(4,4′‐bi‐1,3‐benzodioxole)‐5,5′‐diylbis(diphenylphosphine)]. The mode of enantioselection is discussed based on transition state models involving six‐membered pericyclic structures.magnified image
• Inter- and intramolecular Mitsunobu reaction and metal complexation study: synthesis of S-amino acids derived chiral 1,2,3,4-tetrahydroquinoxaline, benzo-annulated [9]-N3 peraza, [12]-N4 peraza-macrocycles
  作者：Krishnananda Samanta、Nitin Srivastava、Satyen Saha、Gautam Panda

  DOI：10.1039/c1ob06304a

  日期：——

  Substituted 1,2,3,4-tetrahydroquinoxaline, benzo-annulated unsymmetrical chiral [9]-N3 peraza, and [12]-N4 peraza-macrocycles have been synthesized employing an inter- and intramolecular Mitsunobu reaction from an amino acid derived common synthetic intermediate 3. The metal complexation study of these macrocycles has been investigated by UV-visible spectroscopic technique with binding constant (Kb) value 1.84 × 103 dm3 mol−1 using the Benesi–Hildebrand equation and a Gibbs free energy (ΔG) −19.4 kJ mol−1 at 35 °C for 14d with Co2+. The binding properties of the metal were dependent on the structure of polyaza-macrocycles that were confirmed by the DFT optimized structure of two macrocycles. A detailed investigaton of UV-visible spectra of macrocycles and their complete interpretation with the help of TD-DFT along with the frontier molecular orbital calculations are presented.

  合成了替代的1,2,3,4-四氢喹喔啉、苯环附加的不对称手性[9]-N3佩拉扎和[12]-N4佩拉扎大环，采用分子间和分子内的Mitsunobu反应，从氨基酸衍生的共同合成中间体3开始。这些大环的金属配位研究通过紫外-可见光谱技术进行，结合常数（Kb）值为1.84 × 10^3 dm^3 mol−1，使用Benesi–Hildebrand方程，并在35°C下，14天内对于Co2+的吉布斯自由能（ΔG）为-19.4 kJ mol−1。金属的结合特性依赖于聚氮大环的结构，这一点通过DFT优化的两个大环的结构得到确认。详细探讨了大环的紫外-可见光谱及其完整解释，并借助TD-DFT以及前沿分子轨道计算进行了分析。