2-((2,6-diisopropylphenyl)amino)-2-oxoacetic acid | 169772-26-3

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: 2-((2,6-diisopropylphenyl)amino)-2-oxoacetic acid
• 英文别名: 2-[(2,6-diisopropylphenyl)amino]-2-oxoacetic acid；N-(2,6-diisopropylphenyl)-oxamic acid；2-[[2,6-Di(propan-2-yl)phenyl]amino]-2-oxoacetic acid；2-[2,6-di(propan-2-yl)anilino]-2-oxoacetic acid
• CAS: 169772-26-3
• 化学式: C₁₄H₁₉NO₃
• 分子量: 249.31
• InChiKey: YVTXGNXUMNTBDW-UHFFFAOYSA-N

物化性质

• 熔点：
  165.0-165.3 °C(Solv: dichloromethane (75-09-2); hexane (110-54-3))
• 密度：
  1.147±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  18
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  66.4
• 氢给体数：
  2
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2-((2,6-diisopropylphenyl)amino)-2-oxoacetic acid 在 borane-tetrahydrofuran complex 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 4.0h， 生成 N-(4-bromo-2,6-diisopropylphenyl)-N'-(2,6-diisopropylphenyl)ethane-1,2-diamine
  参考文献：
  名称：

  取代的咪唑烷的合成：4,5-二氢-1H-咪唑-3-鎓盐和N-杂环卡宾的碱稳定前体

  摘要：

  目前的工作建立了一种新的合成路线，可产生取代的唑鎓盐。合成了碱稳定的 1-(4-溴-2,6-二异丙基苯基)-3-(2,6-二异丙基苯基)咪唑烷和 1,3-双(4-溴-2,6-二异丙基苯基)咪唑烷，4 -Br 取代基通过 Br/Li 交换或 Pd 催化的交叉偶联反应（Suzuki、Sonogashira 和乙烯基化）转化为各种官能团。通过使用氯苯醌或 N-溴代琥珀酰亚胺氧化取代的咪唑烷，以提供相应的唑鎓盐，它们是 N-杂环卡宾的方便前体。

  DOI：

  10.1002/ejoc.201402364
• 作为产物：
  描述：

  methyl 2-((2,6-diisopropylphenyl)amino)-2-oxoacetate 在 sodium hydroxide 作用下， 以 四氢呋喃 、 水 为溶剂， 反应 2.0h， 以78%的产率得到2-((2,6-diisopropylphenyl)amino)-2-oxoacetic acid
  参考文献：
  名称：

  高通量竞争实验在天冬氨酸定向肽中酪氨酸残基的位点选择性修饰中的应用。

  摘要：

  在本文中，我们报告了铜催化的肽的位点选择性官能化，该肽采用天冬氨酸（Asp）作为天然的导向基序，将O-芳基化位点导向近端酪氨酸（Tyr）残基。通过在高通量反应阵列中进行的一系列竞争研究，确定了在Asp定向的Tyr修饰中对Tyr近端具有高选择性的有效条件。在许多情况下，包括肽-小分子杂交体，在靠近Tyr残基的O-芳基化反应中都实现了良好的位点选择性。

  DOI：

  10.1021/acs.joc.0c01147

文献信息

• Design and synthesis of thioether-imidazolium chlorides as efficient ligands for palladium-catalyzed Suzuki–Miyaura coupling of aryl bromides with arylboronic acids
  作者：Masami Kuriyama、Rumiko Shimazawa、Ryuichi Shirai

  DOI：10.1016/j.tet.2007.06.097

  日期：2007.9

  composed of 0.25–0.025 mol % of [Pd(allyl)Cl]2 and 0.5–0.05 mol % of the thioether-imidazolium chloride 3c was proven to be efficient in the Suzuki–Miyaura cross-coupling reactions of aryl bromides with arylboronic acids.

  已证明由0.25–0.025 mol％的[Pd（烯丙基）Cl] 2和0.5–0.05 mol％的硫醚-咪唑氯化物3c组成的催化剂在芳烃溴化物与芳基硼酸的Suzuki-Miyaura交叉偶联反应中是有效的酸。
• Efficient copper-catalyzed amination of DNA-conjugated aryl iodides under mild aqueous conditions
  作者：Yves Ruff、Frédéric Berst

  DOI：10.1039/c8md00185e

  日期：——

  Herein, we describe the development of copper-catalyzed cross-coupling of DNA-conjugated aryl iodides with aliphatic amines. This protocol leverages a novel ligand, 2-((2,6-dimethoxyphenyl)amino)-2-oxoacetic acid, to effect the transformation in aqueous DMSO, under mild conditions and in air, making it an ideal candidate for the synthesis of DNA-encoded libraries.

  在此，我们描述了铜催化 DNA 缀合的芳基碘化物与脂肪胺交叉偶联的发展。该方案利用新型配体 2-((2,6-二甲氧基苯基)氨基)-2-氧代乙酸，在温和条件下和空气中实现水性 DMSO 中的转化，使其成为 DNA 合成的理想候选者- 编码库。
• Palladium-Catalyzed Hydroxymethylation of Aryl- and Heteroarylboronic Acids using Aqueous Formaldehyde
  作者：Tetsuya Yamamoto、Azamat Zhumagazin、Takuma Furusawa、Ryoji Tanaka、Tetsu Yamakawa、Yohei Oe、Tetsuo Ohta

  DOI：10.1002/adsc.201400845

  日期：2014.11.24

  AbstractCyclometallated NHC palladium complexes prepared from palladium(II) acetate [Pd(OAc)2] and unsymmetrical 1,3‐diarylimidazolinium salts catalyzed the hydroxymethylation of (hetero)arylboronic acids using an excess amount of formalin to afford (hetero)arylmethanols in good to satisfactory yields.magnified image
• Room-Temperature Negishi Cross-Coupling of Unactivated Alkyl Bromides with Alkyl Organozinc Reagents Utilizing a Pd/<i>N</i>-Heterocyclic Carbene Catalyst
  作者：Niloufar Hadei、Eric Assen B. Kantchev、Christopher J. O'Brien、Michael G. Organ

  DOI：10.1021/jo051304c

  日期：2005.10.1

  A high-yielding cross-coupling reaction of unactivated alkyl bromides possessing beta-hydrogens with alkylzinc halides utilizing a Pd/N-heterocyclic carbene (NHC) catalyst at room temperature is described. A variety of Pd sources, Pd-2(dba)(3), Pd(OAc)(2), or PdBr2, with the commercially available ligand precursor 1,3-bis(2,6-diisopropylphenyl)imidazolium chloride (IPr center dot HCl) successfully coupled 1-bromo-3-phenylpropane with n-butylzinc bromide in THF/NMP. An investigation of different NHC precursors showed that the bulky 2,6-diisopropylphenyl moiety was necessary to achieve high coupling yields (75-85%). The corresponding ethyl analogue was moderately active (11%). A range of unsymmetrical NHC precursors were prepared and evaluated. The ligand precursor containing one 2,6-diisopropylphenyl and one 2,6-diethylphenyl afforded the coupling product in 47% yield, clearly suggesting a direct relationship between the steric topography created by the flanking N-substituents and catalyst activity. Under optimal conditions, a number of alkyl bromides and alkylzinc halides possessing common functional groups (amide, nitrile, ester, acetal, and alkyne) were effectively coupled (61-92%). It is noteworthy that beta-substituted alkyl bromides and alkylzinc halides successfully underwent cross-coupling. Also, under these conditions alkyl chlorides were unaffected.
• Reactivity of Carbamoyl Radicals. A New, General, Convenient Free-Radical Synthesis of Isocyanates from Monoamides of Oxalic Acid
  作者：Francesco Minisci、Francesca Fontana、Fausta Coppa、Yong Ming Yan

  DOI：10.1021/jo00122a020

  日期：1995.9

  A new, general, simple synthesis of isocyanates was developed by oxidation of monoamides of oxalic acid with peroxydisulfate catalyzed by Ag and Cu salts. The reaction was carried out in a two-phase system (water and an organic solvent), and it is suitable also for practical applications, due to the simple experimental conditions and the inexpensive as well as nontoxic reagents. The first example of homolytic intramolecular aromatic carbamoylation is also reported.