1,1-difluoro-3,3-dimethyltridec-1-en-4-one

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1,1-difluoro-3,3-dimethyltridec-1-en-4-one
• 英文别名: 1,1-Difluoro-3,3-dimethyltridec-1-en-4-one
• 化学式: C₁₅H₂₆F₂O
• 分子量: 260.368
• InChiKey: NTBXXPCIRLDLPT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.8
• 重原子数：
  18
• 可旋转键数：
  10
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  1,1-difluoro-3,3-dimethyltridec-1-en-4-one 在 potassium hydride 作用下， 以 四氢呋喃 为溶剂， 反应 2.0h， 以91%的产率得到(Z)-5-fluoro-3,3-dimethyl-2-nonylidene-2,3-dihydrofuran
  参考文献：
  名称：

  Nucleophilic 5-endo-trig Cyclization of 3,3-Difluoroallylic Metal Enolates and Enamides: Facile Synthesis of Ring-Fluorinated Dihydroheteroles

  摘要：

  Metal enolates and enamides bearing difluoroallylic moieties underwent nucleophilic 5-endo-trig cyclization, a process considered to be disfavored according to Baldwin's rules. Whereas no C-cyclization was observed in these reactions, O- and N-cyclization proceeded exclusively to afford 5-fluorinated 2-alkylidene-2,3-dihydrofurans and -2,3-dihydropyrroles, respectively.

  DOI：

  10.1055/s-0033-1340857
• 作为产物：
  描述：

  癸酰氯 在 正丁基锂 、 二异丙胺 、 三(二甲胺基)膦 作用下， 以 四氢呋喃 、 乙醚 、 正己烷 为溶剂， 反应 18.5h， 生成 1,1-difluoro-3,3-dimethyltridec-1-en-4-one
  参考文献：
  名称：

  Nucleophilic 5-endo-trig Cyclization of 3,3-Difluoroallylic Ketone Enolates: Synthesis of 5-Fluorinated 2-Alkylidene-2,3-dihydrofurans

  摘要：

  3,3-Difluoroallylic ketones readily undergo nucleophilic 5-endo-trig cyclization through their metal enolates to afford 5-fluorinated 2-alkylidene-2,3-dihydrofurans. O-Cyclization exclusively occurred via intramolecular substitution of the vinylic fluorines.

  DOI：

  10.1055/s-0032-1317709

文献信息

• Heck-type 5-endo-trig cyclizations promoted by vinylic fluorines: Ring-fluorinated indene and 3H-pyrrole syntheses from 1,1-difluoro-1-alkenes
  作者：Junji Ichikawa、Kotaro Sakoda、Jun Mihara、Naotaka Ito

  DOI：10.1016/j.jfluchem.2005.12.023

  日期：2006.5

  Arylpalladium or aminopalladium species bearing a 2,2-difluorovinyl group undergo an unusual 5-endo alkene insertion followed by beta-fluorine elimination. These processes provide a facile access to ring-fluorinated five-membered carbocyclic and heterocyclic compounds starting from an o-(3,3-difluoroallyl)phenyl trifluoromethanesulfonate and 3,3-difluoroallyl ketone O-pentafluorobenzoyloximes. In both systems, the two vinylic fluorine atoms are essential for Heck-type 5-endo-trig cyclizations. (C) 2006 Elsevier B.V All rights reserved.
• Nucleophilic 5-endo-trig Cyclization of 3,3-Difluoroallylic Ketone Enolates: Synthesis of 5-Fluorinated 2-Alkylidene-2,3-dihydrofurans
  作者：Junji Ichikawa、Takeshi Fujita、Kotaro Sakoda、Masahiro Ikeda、Masahiro Hattori

  DOI：10.1055/s-0032-1317709

  日期：——

  3,3-Difluoroallylic ketones readily undergo nucleophilic 5-endo-trig cyclization through their metal enolates to afford 5-fluorinated 2-alkylidene-2,3-dihydrofurans. O-Cyclization exclusively occurred via intramolecular substitution of the vinylic fluorines.
• Nucleophilic 5-endo-trig Cyclization of 3,3-Difluoroallylic Metal Enolates and Enamides: Facile Synthesis of Ring-Fluorinated Dihydroheteroles
  作者：Junji Ichikawa、Takeshi Fujita、Masahiro Ikeda、Masahiro Hattori、Kotaro Sakoda

  DOI：10.1055/s-0033-1340857

  日期：——

  Metal enolates and enamides bearing difluoroallylic moieties underwent nucleophilic 5-endo-trig cyclization, a process considered to be disfavored according to Baldwin's rules. Whereas no C-cyclization was observed in these reactions, O- and N-cyclization proceeded exclusively to afford 5-fluorinated 2-alkylidene-2,3-dihydrofurans and -2,3-dihydropyrroles, respectively.