N,N-diethyl-2,2-difluoro-2-phenylacetamide

• 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: N,N-diethyl-2,2-difluoro-2-phenylacetamide
• 英文别名: N,N-Diethyldifluorophenylacetamide
• 化学式: C₁₂H₁₅F₂NO
• 分子量: 227.254
• InChiKey: AWRIADPVNVXTAA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  16
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  20.3
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2,2,6,6-四甲基哌啶氧化物 、 N,N-diethyl-2,2-difluoro-2-phenylacetamide 在 (1,5-环辛二烯)二(三甲基硅烷基甲基)钯(II) 、 双(2-二苯基磷苯基)醚 作用下， 以 苯 为溶剂， 反应 20.0h， 以91%的产率得到N,N-diethyl-2,2-difluoro-2-((2,2,6,6-tetramethylpiperidin-1-yl)-oxy)acetamide
  参考文献：
  名称：

  在热和光诱导条件下钯（II）二烷基络合物与烷基溴化物反应中单电子途径的证据

  摘要：

  Palladium(II) dialkyl complexes have previously been studied for their formation of alkanes through reductive elimination. More recently, these complexes, especially L2Pd-(CH2TMS)(2) derived from Pd(COD)(CH2TMS)(2), have found general use as palladium(0) precursors for stoichiometric formation of oxidative addition complexes through a two-electron reductive elimination/oxidative addition sequence. Herein, we report evidence for an alternative pathway, proceeding through single-electron elementary steps, when DPEPhosPd(CH2TMS)(2) is treated with an alpha-bromo-alpha,alpha-difluoroacetamide. This new pathway does not take place through a palladium(0) intermediate, neither does it afford the expected oxidative addition complexes. Instead, stoichiometric amounts of carbon-centered alkyl radicals are formed, which can be trapped in high yields either by TEMPO or by an arene, leading to alpha-aryl-alpha,alpha-difluoroacetamides. The same overall transformation takes place under both thermal conditions (70 degrees C) and irradiation with a household light bulb (at 30 degrees C). It is also demonstrated that DPEPhosPdMe(2), made in situ from Pd(TMEDA)Me-2, displays a similar initial reactivity. Finally, electronically and structurally different alkyl bromides were evaluated as reaction partners.

  DOI：

  10.1021/acs.organomet.6b00893
• 作为产物：
  描述：

  chloro-N,N-diethyldifluoroacetamide 在 potassium fluoride 、 C₂₆H₃₉ClNPPd 、 magnesium 作用下， 以 1,4-二氧六环 、 N,N-二甲基甲酰胺 、 甲苯 为溶剂， 反应 32.0h， 生成 N,N-diethyl-2,2-difluoro-2-phenylacetamide
  参考文献：
  名称：

  Pd 催化 α,α-二氟乙酰胺三甲基硅基烯醇化物的 α-芳基化

  摘要：

  我们报道了由含有 P(t-Bu)2Cy 作为配体的空气和湿气稳定的钯环配合物催化的 α,α-二氟-α-(三甲基硅基)乙酰胺与芳基和杂芳基溴的芳基化和杂芳基化。多种电子变化的芳基和杂芳基溴化物经历了这种转化，以高产率提供 α-芳基-α,α-二氟乙酰胺。由于氟化酰胺的亲电性，这种钯催化的交叉偶联反应提供了一个通用平台来生成一系列 α,α-二氟羰基化合物，例如 α-芳基-α,α-二氟酮、-乙醛、-在温和条件下，可以制备乙酸酯、乙酸和二氟烷基衍生物，例如2-芳基-2,2-二氟乙醇和乙胺。

  DOI：

  10.1021/ja508590k

文献信息

• [EN] METAL-CATALYZED COUPLING OF ARYL AND VINYL HALIDES WITH ALPHA, ALPHA-DIFLUOROCARBONYL COMPOUNDS<br/>[FR] COUPLAGE CATALYSÉ MÉTALLIQUE D'HALOGÉNURES D'ARYLE ET DE VINYLE AVEC DES COMPOSÉS ALPHA, ALPHA-DIFLUOROCARBONYLE
  申请人：UNIV CALIFORNIA

  公开号：WO2014165861A1

  公开（公告）日：2014-10-09

  The coupling of aryl, heteroaryl, and vinyl halides with α,α-difluoroketones or silyl ethers or siylenol ethers of α,α-difluoroketones and α,α-difluoroamides and esters are described. Further derivatization of the coupling products (such as ketone cleavage and Baeyer-Villiger oxidation) is also described.

  描述了芳基、杂环基和乙烯卤化物与α，α-二氟酮或硅醚或α，α-二氟酮的硅醚或硅烯醇醚和α，α-二氟酮和α，α-二氟酰胺和酯的偶联。还描述了对偶联产物的进一步衍生化（如酮裂解和巴耶-维利格氧化）。
• FLUORINATING AGENT
  申请人：DAIKIN INDUSTRIES, LTD.

  公开号：US20160332877A1

  公开（公告）日：2016-11-17

  An object of the present invention is to provide a novel substance that has a high reactivity as a fluorinating agent, is effectively used in various fluorination reactions, and is safely handled even in air. As the solution for achieving this object, the present invention provides a complex obtained by reacting bromine trifluoride with at least one metal halide selected from the group consisting of halogenated metals and halogenated hydrogen metals in a nonpolar solvent. This complex serves as a fluorinating agent that provides excellent fluorination performance and that is stable in air.

  本发明的一个目的是提供一种新型物质，作为氟化剂具有高反应性，在各种氟化反应中有效地使用，并且即使在空气中也可以安全处理。为了实现这一目的，本发明提供了一种通过在非极性溶剂中将三氟化溴与来自卤化金属和卤化氢金属组成的金属卤化物中至少一种反应而获得的复合物。这种复合物作为氟化剂具有出色的氟化性能，并且在空气中是稳定的。
• Synthesis, Characterization, and Reactivity of Palladium Fluoroenolate Complexes
  作者：Sophie I. Arlow、John F. Hartwig

  DOI：10.1021/jacs.7b09949

  日期：2017.11.15

  by palladium complexes have been reported, but palladium fluoroenolate intermediates relevant to such reactions have not been isolated or even detected previously. We report the synthesis, structural characterization, and reactivity of a series of C-bound arylpalladium fluoroenolate complexes ligated by monophosphines and bisphosphines. DPPF-ligated arylpalladium fluoroenolate complexes (DPPF = 1,1

  已经报道了由钯配合物催化的芳基与α-氟代羰基化合物的交叉偶联反应，但与这种反应相关的氟烯醇钯中间体以前没有被分离甚至检测到。我们报告了一系列由单膦和双膦连接的 C 结合芳基钯氟烯醇盐配合物的合成、结构表征和反应性。源自单氟酯、二氟酯、二氟酰胺和二氟乙腈的 DPPF 配位芳基氟烯醇化钯复合物 (DPPF = 1,1-双(二苯基膦)-二茂铁) 以高产率进行还原消除。与含有更多吸电子氟烯醇基团和较短 Pd-C(enolate) 键的配合物相比，含有较少吸电子氟烯醇基团和较长 Pd-C(enolate) 键的配合物的还原消除速度更快。这些 C 结合的氟烯醇化物配合物的还原消除速率明显快于类似的三氟甲基配合物的还原消除速率。
• Desulfurizing Difluorination Reaction of Benzyl Sulfides Using IF₅
  作者：Shoji Hara、Tadahito Fukuhara

  DOI：10.1055/s-0028-1087511

  日期：——

  of - ketocarbonyl compounds, 5 and building-block methods. 6 Pummerer-type difluorination of -thiocarbonyl compounds proceeds under mild conditions. However, the removal of the thio group from the products is difficult. The deoxyfluorination reaction of -ketocarbonyl compounds with (diethylamino)sulfur trifluoride (DAST) or Deoxofluor has been frequently used for the synthesis of - difluorocarbonyl

  具有酯、酮、腈或酰胺等官能团的苄基硫化物的脱硫二氟化反应通过与IF5反应进行。因此，可以选择性地获得gem-二氟化合物。1 特别是 αα-二氟羰基化合物，广泛用于生物有机和药物化学的各个领域。2 已经开发了几种合成αα-二氟羰基化合物的方法，例如α-硫代羰基化合物的Pummerer型氟化，3羰基化合物的亲电氟化，2b,4α-酮羰基化合物的脱氧氟化，5和构建-块方法。6 α-硫代羰基化合物的普默尔型二氟化反应在温和条件下进行。然而，从产物中除去硫基是困难的。α-酮羰基化合物与（二乙氨基）三氟化硫（DAST）或 Deoxofluor 的脱氧氟化反应经常用于合成αα-二氟羰基化合物。然而，当该方法用于与α-二酮反应合成αα-二氟酮时，很难区分底物中的两个羰基，并且会发生不希望的副反应，如多氟化反应。5c,d 如多氟化反应。5c,d 如多氟化反应。5c,d
• Copper-Mediated Aerobic Fluoroalkylation of Arylboronic Acids with Fluoroalkyl Iodides at Room Temperature
  作者：Qingqing Qi、Qilong Shen、Long Lu

  DOI：10.1021/ja301705z

  日期：2012.4.18

  A Cu-mediated ligandless aerobic fluoroalkylation of arylboronic acids under mild conditions is described for the first time. The reaction tolerates a wide range of functional groups, allowing for further transformation. Mechanistic studies suggest that [R(f)Cu] is the active Cu species that forms the desired perfluoroalkylarenes and that [R(f)Cu] is generated from [PhCu] by either an oxidative addition/reductive

  首次描述了在温和条件下 Cu 介导的无配体有氧氟烷基化芳基硼酸。该反应耐受范围广泛的官能团，允许进一步转化。机理研究表明，[R(f)Cu] 是形成所需全氟烷基芳烃的活性铜物质，[R(f)Cu] 是通过氧化加成/还原消除机制或通过亲核取代从 [PhCu] 生成的卤素“吃了”中间体。