3,3-difluoro-1-phenylindolin-2-one

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吲哚及其衍生物
• 英文名称: 3,3-difluoro-1-phenylindolin-2-one
• 英文别名: 1-phenyl-3,3-difluorooxindole；3,3-Difluoro-1-phenylindol-2-one
• 化学式: C₁₄H₉F₂NO
• 分子量: 245.228
• InChiKey: BDBBJDOJWQYUPF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  18
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.07
• 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：

  4-甲氧基苯乙烯 、 3,3-difluoro-1-phenylindolin-2-one 在 sodium dihydrogenphosphate dihydrate 、 二叔丁基过氧化物 、 C₆H₁₁BN₂ 、 苯硫酚 作用下， 以 1,4-二氧六环 为溶剂， 反应 24.0h， 以61%的产率得到3-fluoro-3-(4-methoxyphenethyl)-1-phenylindolin-2-one
  参考文献：
  名称：

  4-二甲氨基吡啶-硼基自由基促进的 3,3-二氟羟吲哚的单脱氟烷基化

  摘要：

  实现了 3,3-二氟羟吲哚的选择性单脱氟烷基化。该反应开始于 4-二甲基氨基吡啶-硼基自由基对 3,3-二氟羟吲哚的羰基氧原子的攻击，随后自旋中心位移生成自由基中间体，同时消除了一个氟阴离子。随后对烯烃进行自由基加成，得到一系列 3-烷基-氟羟吲哚产物。该策略提供了获得具有广泛底物范围并耐受多种官能团的 C-3 官能化羟吲哚的途径。

  DOI：

  10.1002/cjoc.202100784
• 作为产物：
  描述：

  1-苯基-1H-吲哚 在 叔丁基过氧化氢 、 N-氟代双苯磺酰胺 作用下， 以 甲苯 、 乙腈 为溶剂， 反应 3.0h， 以40%的产率得到3,3-difluoro-1-phenylindolin-2-one
  参考文献：
  名称：

  Direct Conversion of Indoles to 3,3-Difluoro-2-oxindoles via Electrophilic Fluorination

  摘要：

  3,3-Difluoro-2-oxindoles can be obtained directly from indoles in moderate yields via electrophilic fluorination using N-fluorobenzenesulfonimide as a mild fluorinating reagent. The presence of tell-butyl hydroperoxide during the reaction, together with additional heating after quenching the reaction with triethylamine, is beneficial to the formation of the desired product.

  DOI：

  10.1021/ol302666d

文献信息

• Visible-light photoredox intramolecular difluoroacetamidation: facile synthesis of 3,3-difluoro-2-oxindoles from bromodifluoroacetamides
  作者：Xiao-Jing Wei、Lin Wang、Shao-Fu Du、Li-Zhu Wu、Qiang Liu

  DOI：10.1039/c5ob02121a

  日期：——

  An efficient access to 3,3-difluoro-2-oxindoles has been achieved via intramolecular aminocarbonyldifluoromethyl radical addition to arenes under visible-light irradiation.

  已经通过可见光照射下的分子内氨基羰基二氟甲基自由基加成到芳烃的方式高效合成了3,3-二氟-2-氧代吲哚。
• Solvent Effects: Syntheses of 3,3-Difluorooxindoles and 3-Fluorooxindoles from Hydrazonoindolin-2-one by Selectfluor
  作者：Qiong Yang、Guo-Li Dai、Yu-Ming Yang、Zhuangzhu Luo、Zhen-Yu Tang

  DOI：10.1021/acs.joc.8b00737

  日期：2018.6.15

  Efficient syntheses of 3,3-difluorooxindoles and 3-fluorooxindoles via fluorination of hydrazonoindolin-2-one with Selectfluor are reported. Under different solvent conditions, this method produced 3,3-difluorooxindoles and 3-fluorooxindoles selectively. The broad substrate scope and mild reaction conditions make this transformation a valuable method in drug discovery and development.
• Nucleophilic Di- and Tetrafluorination of Dicarbonyl Compounds
  作者：Rajendra P. Singh、Utpal Majumder、Jean'ne M. Shreeve

  DOI：10.1021/jo0157674

  日期：2001.9.1

  Reactions of various diketo compounds with Deoxofluor [(CH3OCH2CH2)(2)NSF3] have been investigated. When reacted with Deoxofluor, a-diketones, R1COCOR2 (R-1 = R-2 = Ph; R-1 = R-2 = 4-Me-C6H4; R-1 = Ph, R-2 = Me; R-1 = Me, R-2 = Et) (1a-d) formed difluoro derivatives (2a-d) in the presence of a catalytic amount of HF and/or tetrafluoro (3a-d) products depending on the reaction conditions and stoichiometry used. Reactions of beta -diketones, R3COCH2COR4 (R-3 = R-4 = Ph; R-3 = R-4 = Me; R-3 = Me, R-4 = Ph) (4e-g), with Deoxofluor in the presence of a catalytic amount of HF led to the formation of difluoroalkenones as a mixture of E (5e-g) and Z (6e-g) isomers in good yield. Reaction of other diones, R5CO-X-COR6 (R-5 = R-6 = Ph, X =-CH=CH-; R-5 = R-6 = Me, X = -C6H4C6H4-; R-5 = R-6 = Ph, X = -CH2CH2CH2-; R-5 = R-6 = Me, X = -CH2CH2-) (7h-k) with Deoxofluor produced mainly difluoro products (8h-k) with low yields of tertrafluoro derivatives (9h-k). Acyclic alpha -keto amides react poorly to give the corresponding difluoro derivatives, whereas cyclic (alpha -keto amides (101-p) react smoothly under very mild conditions to produce the corresponding difluoro products (111-p) in > 88% isolated yield.
• Copper-Mediated Fluoroalkylation Reactions with Iododifluoroacetamides: Controlling the Selectivity among Cross-Coupling, Intramolecular Cyclization, and Homocoupling Reactions
  作者：Jieming Zhu、Wei Zhang、Laijun Zhang、Jun Liu、Ji Zheng、Jinbo Hu

  DOI：10.1021/jo1005262

  日期：2010.8.20

  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.