2-phenyl-N-[2,3,5,6-tetrafluoro-4-(trifluoromethyl)phenyl]acetamide | 1446442-80-3

• 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: 2-phenyl-N-[2,3,5,6-tetrafluoro-4-(trifluoromethyl)phenyl]acetamide
• CAS: 1446442-80-3
• 化学式: C₁₅H₈F₇NO
• 分子量: 351.223
• InChiKey: VIGAHUOVAMHAQJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4
• 重原子数：
  24
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.13
• 拓扑面积：
  29.1
• 氢给体数：
  1
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  2-phenyl-N-[2,3,5,6-tetrafluoro-4-(trifluoromethyl)phenyl]acetamide 在 碘 、 cesium acetate 、 palladium diacetate 、 碳酸氢钠 作用下， 以 2-甲基-2-丁醇 、 N,N-二甲基甲酰胺 为溶剂， 反应 20.0h， 以95%的产率得到2-(2,6-diiodophenyl)-N-[2,3,5,6-tetrafluoro-4-(trifluoromethyl)phenyl]acetamide
  参考文献：
  名称：

  Pd(II)-Catalyzed C–H Iodination Using Molecular I₂ as the Sole Oxidant

  摘要：

  Pd-catalyzed ortho-C-H iodination directed by a weakly coordinating amide auxiliary using h as the sole oxidant was developed. This reaction is compatible with a wide range of heterocycles including pyridines, imidazoles, oxazoles, thiazoles, isoxazoles, and pyrazoles.

  DOI：

  10.1021/ja4055492
• 作为产物：
  描述：

  苯乙酸 在 草酰氯 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 反应 23.0h， 生成 2-phenyl-N-[2,3,5,6-tetrafluoro-4-(trifluoromethyl)phenyl]acetamide
  参考文献：
  名称：

  Ligand-Enabled Meta-C–H Alkylation and Arylation Using a Modified Norbornene

  摘要：

  2-Carbomethoxynorbornene is identified as a more effective transient mediator to promote a Pd(II)-catalyzed meta-C(sp(2))-H alkylation of amides with various alkyl iodides as well as arylation with previously incompatible aryl iodides. The use of a tailor-made quinoline ligand is also crucial for this reaction to proceed.

  DOI：

  10.1021/jacs.5b08914

文献信息

• (Diacetoxyiodo)benzene-Mediated Oxygenation of Benzylic C(sp³)-H Bonds with<i>N</i>-Hydroxyamides at Room Temperature
  作者：Peng-Cheng Qian、Yu Liu、Ren-Jie Song、Ming Hu、Xu-Heng Yang、Jian-Nan Xiang、Jin-Heng Li

  DOI：10.1002/ejoc.201403616

  日期：2015.3

  A new, metal-free method for the formation of C(sp3)–O bonds was established by PhI(OAc)2-mediated oxygenation of benzylic C(sp3)–H bonds with N-hydroxyamides at room temperature, in which the C(sp3)–H oxidation is activated by a polyflurophenylamide group.

  一种新的无金属形成 C(sp3)-O 键的方法是通过 PhI(OAc)2 介导的苄基 C(sp3)-H 键与 N-羟基酰胺在室温下氧化，其中 C (sp3)–H 氧化由多氟苯基酰胺基团激活。
• Ligand-enabled meta-C–H activation using a transient mediator
  作者：Xiao-Chen Wang、Wei Gong、Li-Zhen Fang、Ru-Yi Zhu、Suhua Li、Keary M. Engle、Jin-Quan Yu

  DOI：10.1038/nature14214

  日期：2015.3

  A combination of norbornene and pyridine-type ligand enables commonly used ortho-directing groups to direct meta-C–H activation with palladium catalysts. This manuscript presents a new alternative approach to the selective activation of remote meta-C–H bonds with the aim of C–H functionalization. This method has the advantage over a recently developed protocol involving a U-shaped template in that it does not require the covalent attachment of a complex template. The authors use norbornene as a transient mediator to help achieve bond activation with a simple and common ortho-directing group. The use of a newly developed pyridine-based ligand is crucial for relaying the palladium catalyst to the meta position by norbornene following initial ortho-C–H activation. This work provides a novel approach to arene synthesis that may have applications in the pharmaceuticals industry. Achieving site selectivity in C–H functionalization reactions is a significant challenge, especially when the target C–H bond is distant from existing functional groups1,2,3,4,5. Coordination of a functional group to a metal is often a key driving force and control element in many important reactions including asymmetric hydrogenation6, epoxidation7,8 and lithiation9. Exploitation of this effect has led to the development of a broad range of directed C–H activation reactions10,11,12,13,14. However, these C–H activation methods are limited to proximal C–H bonds, which are spatially and geometrically accessible from the directing functional group. The development of meta-selective C–H functionalizations remains a significant challenge1,2,3,4,5,15,16,17. We recently developed a U-shaped template that can be used to overcome this constraint and have shown that it can be used to selectively activate remote meta-C–H bonds1,2. Although this approach has proved to be applicable to various substrates and catalytic transformations3,4,5, the need for a covalently attached, complex template is a substantial drawback for synthetic applications. Here we report an alternative approach employing norbornene as a transient mediator to achieve meta-selective C–H activation with a simple and common ortho-directing group. The use of a newly developed pyridine-based ligand is crucial for relaying the palladium catalyst to the meta position by norbornene after initial ortho-C–H activation. This catalytic reaction demonstrates the feasibility of switching ortho-selectivity to meta-selectivity in C–H activation of the same substrate by catalyst control.

  降冰片烯和吡啶型配体的结合使常用的正交定向基团能够在钯催化剂的作用下定向活化元-CâH。本手稿介绍了一种以 CâH 功能化为目的，选择性活化远端元-CâH 键的新替代方法。与最近开发的涉及 U 型模板的方案相比，这种方法的优势在于不需要共价连接复杂的模板。作者使用降冰片烯作为瞬时媒介，通过一个简单而常见的正向定向基团帮助实现键活化。在最初的正交-CâH活化之后，使用一种新开发的基于吡啶的配体对于降冰片烯将钯催化剂转移到元位置至关重要。这项工作为炔类化合物的合成提供了一种新方法，可能会应用于制药行业。在 CâH 功能化反应中实现位点选择性是一项重大挑战，尤其是当目标 CâH 键与现有官能团距离较远时1,2,3,4,5。在不对称氢化6 、环氧化7,8 和石化作用9 等许多重要反应中，官能团与金属的配位通常是关键的驱动力和控制元素。利用这一效应开发出了一系列定向 CâH 活化反应10,11,12,13,14。然而，这些 CâH 活化方法仅限于近端 CâH 键，因为这些键在空间和几何上都可以从定向官能团接触到。开发元选择性 CâH 功能化仍然是一项重大挑战1,2,3,4,5,15,16,17。我们最近开发出一种 U 型模板，可用于克服这一限制，并证明它可用于选择性地激活偏远的元 CâH 键1,2。虽然这种方法已被证明适用于各种底物和催化转化3,4,5，但需要共价连接的复杂模板是合成应用的一个重大缺陷。在此，我们报告了一种采用降冰片烯作为瞬时介质的替代方法，通过一个简单而常见的正向定向基团实现元选择性 CâH 活化。使用一种新开发的基于吡啶的配体对于钯催化剂在最初的正交-CâH活化后通过降冰片烯转接到元位置至关重要。这一催化反应证明了通过催化剂控制将同一底物的 CâH 活化的正选择性转换成元选择性的可行性。
• Palladium-catalyzed direct ortho-alkynylation of aryl acetamides with low catalyst loading
  作者：Wenjing Li、Hailong Liu、Xue Chen、Shun Li、Renyin Zheng、Chunchun Zhang、Xueli Zheng、Maolin Yuan、Ruixiang Li、Haiyan Fu、Hua Chen

  DOI：10.1016/j.tetlet.2019.06.003

  日期：2019.7

  The palladium-catalyzed alkynylation of phenylacetic acid derivatives using 4-CF3C6F4NH2 as the auxiliary is described. The reaction efficiency can be greatly promoted by pyridine ligand, which enables the reaction to proceed at a catalyst loading as low as 1 mol%. Various functional groups are tolerated under the reaction conditions. The kinetic studies show that the rate of the reaction is first

  描述了使用4-CF 3 C 6 F 4 NH 2作为辅助剂的钯催化的苯乙酸衍生物的炔基化反应。吡啶配体可以大大提高反应效率，这使得反应可以在低至1 mol％的催化剂负载下进行。在反应条件下容许各种官能团。动力学研究表明，在苯乙酰胺中，反应速率为一级反应，吡啶配体的组合中的Pd（OAc）2提供了高度耐用且有效的催化剂。
• 钯催化的间位芳基化反应及其在维罗非尼类似物合成中的应用
  申请人：陕西科技大学

  公开号：CN111217654A

  公开（公告）日：2020-06-02

  本发明为一种钯催化的间位芳基化反应及其在维罗非尼类似物合成中的应用，其克服了现有技术中反应中会引入副产物，无法直接合成，生产成本较高的问题，实现过渡金属催化的直接C‑H活化转化，可控、精准、高效，合成过程无需惰性气体保护，操作简单，生产成本低，环境污染小。本发明采用的技术方案为：以芳环类化合物0.25mmol作为底物，以浓度为10mol％的醋酸钯为催化剂，降冰片烯类1～1.5当量作为媒介，加入添加剂3equiv，并加入浓度为5mol％～10mol％的配体和1mL三氟甲苯以及二氯乙烷的溶剂，通过与芳基卤代物0.38mmol偶联，在80～120℃下反应12～24h，得到7‑氮杂吲哚5位芳基化产物5‑碘‑7‑氮杂吲哚。