N-benzyl-2,2-difluoro-2-iodoacetamide | 1239497-28-9

• 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-benzyl-2,2-difluoro-2-iodoacetamide
• CAS: 1239497-28-9
• 化学式: C₉H₈F₂INO
• 分子量: 311.07
• InChiKey: MGBVTSIWAJQTIT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  14
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.22
• 拓扑面积：
  29.1
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  N-benzyl-2,2-difluoro-2-iodoacetamide 在 1,1'-双(二苯基膦)二茂铁 、 硼烷四氢呋喃络合物 、 palladium diacetate 、 sodium phosphate 作用下， 以 四氢呋喃 、 乙腈 为溶剂， 70.0~100.0 ℃ 、1.0 MPa 条件下， 反应 21.0h， 生成 N-benzyl-3,3-difluoropiperidine
  参考文献：
  名称：

  烯烃的二氟烷基化羰基化获得含羰基二氟的杂环：吉格列汀的便捷合成

  摘要：

  氟化杂环化合物在制药和农用化学工业中发挥着至关重要的作用。因此，仍然迫切需要快速有效地构建氟化杂环。在此，首次开发了通过钯催化实现的未活化烯烃和乙烯气体的二氟烷基化羰基化环化反应，用于合成 α-羰基二氟修饰的戊二酰亚胺。该程序也可应用于 GeMigliptin 的合成，GeMigliptin 是一种批准用于治疗 2 型糖尿病的药物。

  DOI：

  10.1007/s11426-022-1439-1
• 作为产物：
  描述：

  在 水 、 碳酸氢钠 、 sodium sulfite 、 碘 、 potassium iodide 作用下， 以 水 为溶剂， 反应 4.0h， 生成 N-benzyl-2,2-difluoro-2-iodoacetamide
  参考文献：
  名称：

  Copper-Mediated Fluoroalkylation Reactions with Iododifluoroacetamides: Controlling the Selectivity among Cross-Coupling, Intramolecular Cyclization, and Homocoupling Reactions

  摘要：

  Cu-mediated fluoroalkylation reactions with iododifluoroacetamides I have been systematically investigated. It was found that three types of reactions may coexist in Cu-mediated reactions between iododifluoroacetamides and aryl/alkenyl iodides: cross-coupling, intramolecular cyclization, and homocoupling reactions. The selectivity among these three types of reactions could be controlled by tuning the substituents on the nitrogen atom of iododifluoroacetamides, and/or by removing the cross-coupling reaction partner (aryl/alkenyl halides). The general rule is as follows: (a) in the presence of proper aryl/alkenyl iodides, the cross-coupling products 2 (or 6) are generally formed as the major products; (b) in the absence of aryl/alkenyl iodides, and when R-1 = alkyl and R-2 = aryl groups, or when R-1 = R-2 = aryl groups, the intramolecular cyclization products 3 can be formed predominantly; and (c) in the absence of aryl/alkenyl iodides, and when R-1 = R-2 = alkyl groups, or when R-1 = H and R-2 = alkyl, aryl groups, the homocoupling products 4 can be formed dominantly. Our experimental results also indicate that in many cases when cross-coupling, homocoupling, and intramolecular cyclization reactions coexist in the Cu-mediated reaction system, the reactivity decreases in the following order: cross-coupling > intramolecular cyclization > homocoupling.

  DOI：

  10.1021/jo1005262

文献信息

• Cu-Catalyzed Arylation of Bromo-Difluoro-Acetamides by Aryl Boronic Acids, Aryl Trialkoxysilanes and Dimethyl-Aryl-Sulfonium Salts: New Entries to Aromatic Amides
  作者：Satenik Mkrtchyan、Michał Jakubczyk、Suneel Lanka、Michael Pittelkow、Viktor O. Iaroshenko

  DOI：10.3390/molecules26102957

  日期：——

  copper-catalyzed direct arylation. Readily available and structurally simple aryl precursors such as aryl boronic acids, aryl trialkoxysilanes and dimethyl-aryl-sulfonium salts were used as the source for the aryl substituents. The scope of the reactions was tested, and the reactions were insensitive to the electronic nature of the aryl groups, as both electron-rich and electron-deficient aryls were successfully

  我们描述了一种以机制为导向的合成方法发现，该方法能够利用铜催化的直接芳基化从 2-溴-2,2-二氟乙酰胺制备芳香酰胺。使用易于获得且结构简单的芳基前体，例如芳基硼酸、芳基三烷氧基硅烷和二甲基芳基锍盐作为芳基取代基的来源。测试了反应的范围，并且反应对芳基的电子性质不敏感，因为富电子和缺电子的芳基都被成功引入。多种 2-溴-2,2-二氟乙酰胺（作为脂肪族或芳香族仲酰胺或叔酰胺）在开发的条件下也具有反应性。所描述的合成方案显示出优异的效率，并成功用于以良好到优异的产率快速制备各种芳香酰胺。反应规模扩大至克级。
• AMINE-BORANES AS BIFUNCTIONAL REAGENTS FOR DIRECT AMIDATION OF CARBOXYLIC ACIDS
  申请人：Purdue Research Foundation

  公开号：US20220055983A1

  公开（公告）日：2022-02-24

  The present invention generally relates to a process for selective and direct activation and subsequent amidation of aliphatic and aromatic carboxylic acids to afford an amide R 3 CONR 1 R 2 . That the process is capable of delivering gaseous or low-boiling point amines provides a major advantage over existing methodologies, which involves an intermediate of triacyloxyborane-amine complex [(R 3 CO 2 ) 3 —B—NHR 1 R 2 ]. This procedure readily produces primary, secondary, and tertiary amides, and is compatible with the chirality of the acid and amine involved. The preparation of known pharmaceutical molecules and intermediates has also been demonstrated.

  本发明通常涉及一种选择性和直接激活以及随后酰胺化脂肪族和芳香族羧酸的过程，从而得到一种酰胺R3CONR1R2。该过程能够提供气态或低沸点胺，相对于现有方法而言具有重大优势，该方法涉及三酰氧硼胺复合物的中间体[(R3CO2)3—B—NHR1R2]。该程序能够轻松产生一次、二次和三次酰胺，并且与所涉及的酸和胺的手性兼容。已经证明了已知药物分子和中间体的制备。
• Phototriggered Fluoroalkylation/Cyclization of Unactivated 1-Acryloyl-2-cyanoindoles: Synthesis of RCOCF₂-Substituted Pyrrolo[1,2-<i>a</i>]indolediones
  作者：Weixian Lv、Pengyuan Yang、Jinwei Yuan、Jiayi Li、Mengran Liang、Yitong Liu、Dongliang Xing、Liangru Yang

  DOI：10.1021/acs.joc.3c02986

  日期：2024.3.1

  A photochemical approach toward RCOCF2-substituted pyrrolo[1,2-a]indolediones was developed by the radical cascade difluoroalkylation/cyclization reaction of unactivated 1-acryloyl-2-cyanoindoles with ethyl iododifluoroacetate or iododifluoramides under visible-light irradiation. This transition-metal- and photosensitizer-free protocol afforded diverse difluoroalkylated pyrrolo[1,2-a]indolediones in

  通过未活化的1-丙烯酰基-2-氰基吲哚与碘二氟乙酸乙酯或碘二氟酰胺在可见光照射下的自由基级联二氟烷基化/环化反应，开发了一种制备RCOCF 2 -取代的吡咯并[ 1,2 -a]吲哚二酮的光化学方法。这种不含过渡金属和光敏剂的方案在温和的反应条件下以中等至良好的收率提供了多种二氟烷基化吡咯并[1,2- a ]吲哚二酮。最吸引人的是，该反应可以在阳光照射下顺利进行，这为二氟烷基化吡咯并[1,2- a ]吲哚二酮开辟了一条新途径。
• Synthesis of Azo-Substituted Bicyclo[1.1.1]pentanes (BCPs) via Base-Promoted Halogen Atom Transfer
  作者：Yanchuang Zhao、Jing Zhang、Zhi-Jin Zhan、Qiujin Fan、Xu-Qiong Xiao、Ying Bai、Shao-Fei Ni、Xinxin Shao

  DOI：10.1021/acs.orglett.4c01546

  日期：2024.5.24

  Because of the three-dimensional bioisosteric feature, bicyclo[1.1.1]pentylamines (BCPAs) are valuable scaffolds in synthetic chemistry and medicinal chemistry. Here, we report a Halogen Atom Transfer (XAT) mediated radical C–N coupling between C3-iodo-BCPs and diazonium salts in the presence of base. Similarly, a multicomponent reaction (MCR) enables the simultaneous construction of the C–C bond and

  由于三维生物等排特征，双环[1.1.1]戊胺（BCPA）是合成化学和药物化学中有价值的支架。在这里，我们报告了在碱存在下，C3-碘-BCP 和重氮盐之间的卤素原子转移（XAT）介导的自由基 C-N 偶联。类似地，多组分反应（MCR）可以同时构建 C-C 键和 C-N 键。还探索了重氮盐的多功能作用。