2,2-difluoro-2-iodo-1-morpholinoethanone | 1239497-17-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 恶嗪烷类
• 英文名称: 2,2-difluoro-2-iodo-1-morpholinoethanone
• 英文别名: 2,2-difluoro-2-iodo-1-morpholin-4-ylethanone
• CAS: 1239497-17-6
• 化学式: C₆H₈F₂INO₂
• 分子量: 291.036
• InChiKey: KYULVQFDXAHBGX-UHFFFAOYSA-N

物化性质

• 沸点：
  315.1±42.0 °C(Predicted)
• 密度：
  1.945±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.8
• 重原子数：
  12
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  29.5
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  2,2-difluoro-2-iodo-1-morpholinoethanone 在 铜 作用下， 以 二甲基亚砜 为溶剂， 反应 8.0h， 以47%的产率得到2,2,3,3-Tetrafluoro-1,4-dimorpholin-4-ylbutane-1,4-dione
  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
• 作为产物：
  描述：

  1,1-difluoro-2-morpholin-4-yl-2-oxo-ethanesulfonyl fluoride 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 2,2-difluoro-2-iodo-1-morpholinoethanone
  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

• Visible Light-Promoted Phosphine-Catalyzed Difluoroalkylation of Arenes and Heterocycles
  作者：Heng Lu、Dong-yu Wang、Ao Zhang

  DOI：10.1021/acs.joc.9b02882

  日期：2020.1.17

  A visible light-promoted difluoroalkylation reaction of arenes or heterocycles, using triaryl phosphine as the catalyst and difluoroalkyl iodide as the alkylating agent, is presented. The strategy is highlighted by photocatalyst-free, mild reaction conditions and a broad substrate scope. Mechanistic experiments indicate that this reaction involves a radical-chain process that is initiated by an electron

  提出了使用三芳基膦作为催化剂和二氟烷基碘化物作为烷基化剂的芳烃或杂环的可见光促进的二氟烷基化反应。无光催化剂，温和的反应条件和广泛的底物范围突出了该策略。机理实验表明，该反应涉及自由基链过程，该自由基链过程由二氟烷基碘和膦形成的电子供体-受体配合物引发。
• Fluoroalkylation–Borylation of Alkynes: An Efficient Method To Obtain (<i>Z</i>)-Tri- and Tetrasubstituted Fluoroalkylated Alkenylboronates
  作者：Wen-Hao Guo、Hai-Yang Zhao、Zhi-Ji Luo、Shu Zhang、Xingang Zhang

  DOI：10.1021/acscatal.8b02842

  日期：2019.1.4

  Efficient methods for the synthesis of fluoroalkylated alkenylboronates are very limited, despite their importance in modern organic synthesis. Herein, we report a palladium-catalyzed trans-fluoroalkylation–borylation of alkynes with fluoroalkyl iodides and B2pin2. The reaction tolerates a series of difluoroalkyl iodides and perfluoroalkyl iodides and can enable coupling with a variety of alkynes,

  尽管在现代有机合成中很重要，但合成氟烷基化烯基硼酸酯的有效方法非常有限。在本文中，我们报道了炔烃与氟代烷基碘化物和B 2 pin 2的钯催化反式-氟代烷基化-硼化。该反应可耐受一系列二氟烷基碘和全氟烷基碘，并且可以与各种炔烃偶联，包括内部和末端炔烃，具有高效，高官能团相容性以及高区域选择性和立体选择性。初步的机理研究表明，反式氟烷基化的烯基碘是关键中间体，其随后进行硼酸酯化以产生反式氟烷基化的烯基硼酸酯。
• Pd-Catalyzed Carbonylative Carboperfluoroalkylation of Alkynes. Through-Space ¹³C–¹⁹F Coupling as a Probe for Configuration Assignment of Fluoroalkyl-Substituted Olefins
  作者：Sylwester Domański、Olga Staszewska-Krajewska、Wojciech Chaładaj

  DOI：10.1021/acs.joc.7b01236

  日期：2017.8.4

  A four-component Pd-catalyzed protocol for direct synthesis of perfluoroalkyl-substituted enones is reported. Under mild conditions and low catalyst loading, alkynes, iodoperfluoroalkanes, (hetero)arylboronic acids, and carbon monoxide are assembled into highly elaborate products with good yields and excellent regio- and stereoselectivities. The configuration of the products was confirmed by the observation

  报道了直接合成全氟烷基取代的烯酮的四组分钯催化方案。在温和条件下和低催化剂负载量下，炔烃，碘全氟烷烃，（杂）芳基硼酸和一氧化碳被组装成高度精制的产品，并具有良好的收率以及出色的区域和立体选择性。通过观察常规13 C NMR光谱可观察到贯穿空间的13 C - 19 F偶合，证实了产品的构型。
• 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。