trans-1,1,1-Trifluorotetradec-3-en-2-one

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: trans-1,1,1-Trifluorotetradec-3-en-2-one
• 英文别名: (E)-1,1,1-trifluorotetradec-3-en-2-one
• 化学式: C₁₄H₂₃F₃O
• 分子量: 264.331
• InChiKey: RQNYBNPQIMPNQG-VAWYXSNFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.7
• 重原子数：
  18
• 可旋转键数：
  10
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.79
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  trans-1,1,1-Trifluorotetradec-3-en-2-one 在 甲醇 、 sodium tetrahydroborate 、 bis{rhodium[3,3'-(1,3-phenylene)bis(2,2-dimethylpropanoic acid)]} 、 三氟化硼乙醚 、 sodium hydride 作用下， 以 氯仿 、 乙酸乙酯 、 mineral oil 为溶剂， 反应 14.0h， 生成 3-(dodec-1-en-1-yl)-3-(trifluoromethyl)-1,2,3,6-tetrahydropyridine
  参考文献：
  名称：

  Controllable Skeletal and Peripheral Editing of Pyrroles with Vinylcarbenes

  摘要：

  The skeletal editing of azaarenes through insertion, deletion, or swapping of single atoms has recently gained considerable momentum in chemical synthesis. Here, we describe a practical skeletal editing strategy using vinylcarbenes in‐situ generated from trifluoromethyl vinyl N‐triftosylhydrazones, leading to the first dearomative skeletal editing of pyrroles through carbon‐atom insertion. Furthermore, depending on the used catalyst and substrate, three types of peripheral editing reactions of pyrroles are also disclosed: α‐ or γ‐selective C–H insertion, and [3+2] cycloaddition. These controllable molecular editing reactions provide a powerful platform for accessing medicinally relevant CF3‐containing N‐heterocyclic frameworks, such as 2,5‐dihydropyridines, piperidines, azabicyclo[3.3.0]octadienes, and allylated pyrroles from readily available pyrroles. Mechanistic insights from experiments and density functional theory (DFT) calculations shed light on the origin of substrate‐ or catalyst‐controlled chemo‐ and regioselectivity as well as the reaction mechanism.

  DOI：

  10.1002/anie.202401359
• 作为产物：
  描述：

  1,1,1-trifluorotetradec-3-yn-2-one 在 lithium aluminium tetrahydride 、 戴斯-马丁氧化剂 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 11.0h， 生成 trans-1,1,1-Trifluorotetradec-3-en-2-one
  参考文献：
  名称：

  Synthesis of and Analysis of Thiol Additions to .beta.-Alkyl-.alpha.,.beta.-unsaturated Trifluoromethyl Ketones

  摘要：

  A series of beta-alkyl-alpha,beta-unsaturated trifluoromethyl ketones have been prepared from the corresponding alpha-acetylenic trifluoromethyl ketones. The addition of sulfur nucleophiles was shown by chemical and F-19 NMR studies to proceed exclusively by 1,4-addition with no indication of any 1,2-addition products. The unsaturated trifluoromethyl ketones have been shown to be effective inhibitors of rat cytosolic glutathione-S-transferase.

  DOI：

  10.1021/jo00084a009

文献信息

• Synthesis of and Analysis of Thiol Additions to .beta.-Alkyl-.alpha.,.beta.-unsaturated Trifluoromethyl Ketones
  作者：Russell J. Linderman、Eric A. Jamois、Scott D. Tennyson

  DOI：10.1021/jo00084a009

  日期：1994.3

  A series of beta-alkyl-alpha,beta-unsaturated trifluoromethyl ketones have been prepared from the corresponding alpha-acetylenic trifluoromethyl ketones. The addition of sulfur nucleophiles was shown by chemical and F-19 NMR studies to proceed exclusively by 1,4-addition with no indication of any 1,2-addition products. The unsaturated trifluoromethyl ketones have been shown to be effective inhibitors of rat cytosolic glutathione-S-transferase.
• Controllable Skeletal and Peripheral Editing of Pyrroles with Vinylcarbenes
  作者：Yong Yang、Qingmin Song、Paramasivam Sivaguru、Zhaohong Liu、Dan Shi、Tian Tian、Graham de Ruiter、Xihe Bi

  DOI：10.1002/anie.202401359

  日期：——

  The skeletal editing of azaarenes through insertion, deletion, or swapping of single atoms has recently gained considerable momentum in chemical synthesis. Here, we describe a practical skeletal editing strategy using vinylcarbenes in‐situ generated from trifluoromethyl vinyl N‐triftosylhydrazones, leading to the first dearomative skeletal editing of pyrroles through carbon‐atom insertion. Furthermore, depending on the used catalyst and substrate, three types of peripheral editing reactions of pyrroles are also disclosed: α‐ or γ‐selective C–H insertion, and [3+2] cycloaddition. These controllable molecular editing reactions provide a powerful platform for accessing medicinally relevant CF3‐containing N‐heterocyclic frameworks, such as 2,5‐dihydropyridines, piperidines, azabicyclo[3.3.0]octadienes, and allylated pyrroles from readily available pyrroles. Mechanistic insights from experiments and density functional theory (DFT) calculations shed light on the origin of substrate‐ or catalyst‐controlled chemo‐ and regioselectivity as well as the reaction mechanism.