methyl 2-((3,5-bis(trifluoromethyl)phenyl)amino)-2-phenylacetate | 1605291-11-9

• 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: methyl 2-((3,5-bis(trifluoromethyl)phenyl)amino)-2-phenylacetate
• 英文别名: Phenyl[3,5-bis(trifluoromethyl)anilino]acetic acid methyl ester；methyl 2-[3,5-bis(trifluoromethyl)anilino]-2-phenylacetate
• CAS: 1605291-11-9
• 化学式: C₁₇H₁₃F₆NO₂
• 分子量: 377.286
• InChiKey: ZSYVNPQTVKPSMF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.3
• 重原子数：
  26
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.24
• 拓扑面积：
  38.3
• 氢给体数：
  1
• 氢受体数：
  9

反应信息

• 作为产物：
  描述：

  a-叠氮基-苯乙酸甲酯 在 dirhodium tetraacetate 、 六氟乙酰丙酮化铜的水合物 作用下， 以 甲苯 为溶剂， 反应 21.5h， 生成 methyl 2-((3,5-bis(trifluoromethyl)phenyl)amino)-2-phenylacetate
  参考文献：
  名称：

  铜催化亚砜基sulf的NH插入反应

  摘要：

  描述了铜（II）作为苯胺和α-羰基亚砜基鎓盐之间NH插入反应的有效催化剂的首次用途。通过简单，快速的实验程序，获得了39种芳基甘氨酸衍生物，收率高达97％。

  DOI：

  10.1016/j.tet.2020.131313

文献信息

• Synthesis and catalytic activity of μ-oxo ruthenium(IV) porphyrin species to promote amination reactions
  作者：Paolo Zardi、Daniela Intrieri、Daniela Maria Carminati、Francesco Ferretti、Piero Macchi、Emma Gallo

  DOI：10.1142/s1088424616500814

  日期：2016.8

  of their analogous reactivity towards aryl azides to give the same catalytically active bis-imido species RuVI(TPP)(ArN)2. The reaction of [RuIV(TPP)(OCH[Formula: see text]]2O with Ph3CN3 or (CH[Formula: see text]SiN3 afforded [RuIV(TPP)(N[Formula: see text]]2O which was fully characterised, its molecular structure was also determined by single crystal X-ray analysis.

  这项工作描述了钌（IV）的合成[化学式：见正文]-通式[Ru]-氧卟啉配合物四(TPP)(X)]2O 已被用作使用芳基叠氮化物（ArN[公式：见正文]作为氮烯源的氮烯转移反应的催化剂。收集的数据表明[Ru的催化效率四(TPP)(OCH[公式：见正文]]2O与Ru相当二(TPP)CO 因为它们对芳基叠氮化物具有类似的反应性，从而产生相同的催化活性双亚氨基物质 Ru六(TPP)(ArN)2. [Ru的反应四(TPP)(OCH[公式：见正文]]2O 与 Ph3中国3或 (CH[公式：见正文]SiN3提供 [Ru四(TPP)(N[公式：见正文]]2完全表征的O，其分子结构也通过单晶X射线分析确定。
• Comparative Study of the Catalytic Amination of Benzylic C–H Bonds Promoted by Ru(TPP)(py) ₂ and Ru(TPP)(CO)
  作者：Gabriele Manca、Carlo Mealli、Daniela Maria Carminati、Daniela Intrieri、Emma Gallo

  DOI：10.1002/ejic.201500656

  日期：2015.10

  the toluene substrate (PhCH3). Conversely, by staying on the singlet potential-energy surface, 6S can undergo dissociation of the pyridine ligand to form [Ru](NR). This complex can activate another RN3 molecule to form the bis-imido compound [Ru](NR)2, which is also catalytically active. At this point, the mechanism becomes independent of the nature of the original ligand L coordinated to [Ru].

  结合实验和基于 DFT 的理论分析阐明了轴向配体 L 对 Ru(卟啉)L 配合物在促进有机叠氮化物 (RN3) 对苄基 C-H 键的胺化方面的催化活性的影响。实验数据表明，Ru(TPP)(CO) (1) (TPP = 四苯基卟啉的二价阴离子) 的催化活性与 Ru(TPP)(py)2 (2) (py = 吡啶) 的催化活性相当。DFT 模型揭示了 2 可以被视为一种前催化剂，它在一个吡啶配体的吸能损失后变得活跃，得到不饱和物质 [Ru](py) (11) [Ru] = Ru(卟吩)}。该复合物将与 RN3 反应得到单亚胺单线态复合物 [Ru](py)(NR)S (6S)，它可以很容易地转化为在亚氨基 N 原子上具有双自由基特征的三线态异构体 6T。随后苄胺 PhCH2NHR 的形成是通过甲苯底物 (PhCH3) 的一个 C-H 键的自由基均裂活化而发生的。相反，通过停留在单线态势能表面，6S
• Rhodium(II)-Catalyzed N–H Insertions of Carbenes under Mechanochemical Conditions
  作者：Sourav Biswas、Carsten Bolm

  DOI：10.1021/acs.orglett.4c00216

  日期：2024.2.23

  Under mechanochemical conditions in a mixer mill, Rh2(OAc)4 catalyzes the reaction between aryldiazoesters and anilines to give α-amino esters. The process proceeds under mild conditions and is insensitive to air. It is solvent-free and scalable. A broad substrate scope, short reaction times, operational simplicity, and good functional group tolerance are additional salient features of this protocol

  在混合研磨机中的机械化学条件下，Rh 2 (OAc) 4催化芳基重氮酯和苯胺之间的反应，生成 α-氨基酯。该过程在温和的条件下进行，并且对空气不敏感。它是无溶剂且可扩展的。广泛的底物范围、短的反应时间、操作简单性和良好的官能团耐受性是该协议的其他显着特征。
• Glycoporphyrin Catalysts for Efficient C–H Bond Aminations by Organic Azides
  作者：Giorgio Tseberlidis、Paolo Zardi、Alessandro Caselli、Damiano Cancogni、Matteo Fusari、Luigi Lay、Emma Gallo

  DOI：10.1021/acs.organomet.5b00436

  日期：2015.8.10

  We report herein the synthesis of new glycoporphyrin ligands which bear a glucopyranoside derivative on each meso-aryl moiety of the porphyrin skeleton. The saccharide unit is directly conjugated to the porphyrin or a triazole spacer is placed between the carbohydrate and porphyrin ring. The obtained glycoporphyrin ligands were employed to synthesize cobalt(II), ruthenium(II), and iron(III) complexes which were tested as catalysts of C-H bond aminations by organic azides. Two of the synthesized complexes were very efficient in promoting catalytic reactions, and the results achieved indicated that ruthenium and iron complexes show an interesting complementary catalytic activity in several amination reactions. The eco-friendly iron catalyst displayed very good chemical stability in catalyzing the amination reaction for three consecutive runs without losing catalytic activity.
• Synthesis of Biologically Relevant Compounds by Ruthenium Porphyrin Catalyzed Amination of Benzylic C–H Bonds
  作者：Paolo Zardi、Alessandro Caselli、Piero Macchi、Francesco Ferretti、Emma Gallo

  DOI：10.1021/om500064d

  日期：2014.5.12

  Herein we report the catalytic activity of ruthenium porphyrin complexes to promote the amination of benzylic C-H bonds by aryl azides, yielding alpha- and beta-amino esters. The catalytic methodology is also effective to synthesize two derivatives of methyl L-3-phenyllactate in order to convert one of them into the corresponding beta-lactam. The catalytic experimental conditions have been optimized on the basis of a preliminary mechanistic investigation which underlines the pivotal role of the substrate concentration to maximize the reaction productivity.