フッ素がアルキル基に変換される.
Montserrat Rueda-Becerril1, Claire Chatalova Sazepin, Joe C T Leung
1Chemistry Department, University of British Columbia , 2036 Main Mall, Vancouver, British Columbia V6T 1Z1, Canada.
Journal of the American Chemical Society
|February 11, 2012
まとめ
アルキルラジカルのためのフッ素源としてN-フッ素ベンゼンスルフォニミドを用いた選択的アルキルフッ素化のための新しい方法が開発されました. この画期的な発見は,医薬品用のフッ素を含む化合物を合成するためのより安全で,より汎用的なアプローチを提供します.
科学分野:
- 有機化学 オーガニック・ケミストリー
- 薬用化学 薬用化学について
- 合成方法論 合成方法論
背景:
- フッ素を含む医薬品の需要は,高度な合成技術の必要性を高めています.
- 従来のフッ素化方法は,しばしばイオン性フッ素源 (F(-) またはF(+)) を使用します.
- ラジカル・フッ素化戦略は,安全な原子フッ素 (F(•)) の供給源の不足によって制限されています.
研究 の 目的:
- アルキルラジカルの選択的化のための新しい安全で効果的な方法を開発する.
- オーガニック分子にフッ素を導入するための合成ツールボックスを拡張し,特に医薬品の用途のために.
主な方法:
- フッ素移転剤としてN-フッ素ベンゼンスルフォニミドを使用した.
- この方法を様々なアルキルラジカルに適用した: プライマリ,セカンダリー,サーチアリー,ベンジル,ヘテロ原子安定化.
- 潜在的反応剤の改変と反応条件を調査するための計算計算を行いました.
主要な成果:
- アルキルラジカル・フッ素化における広範な適用性を成功裏に達成しました.
- N-fluorobenzenesulfonimideの有効性を,様々な種類の急性物質に対するフッ素源として実証した.
- 計算分析により,極性介質のための有望なフッ素含有イオン反応剤が特定されました.
結論:
- 開発されたラジカルアルキル化アプローチは,強力な新しい合成変換を提供します.
- この方法は,伝統的な多段階合成に価値ある代替手段を提供します.
- 将来の作業には,イオン反応剤を使用した極性反応環境への方法論の拡張が含まれる可能性があります.
関連する概念動画
Radical Substitution: Halogenation of Alkanes and Alkyl Substituents
9.8K
In the presence of heat or light, alkanes react with molecular halogens to form alkyl halides by a substitution reaction called radical halogenation. This reaction has three steps: initiation, propagation, and termination, as seen in the radical chlorination of methane to produce methyl chloride.
In the initiation step of the reaction, the chlorine molecule undergoes homolytic cleavage in the presence of light or heat, forming two highly reactive chlorine radicals. Propagation occurs in two...
In the initiation step of the reaction, the chlorine molecule undergoes homolytic cleavage in the presence of light or heat, forming two highly reactive chlorine radicals. Propagation occurs in two...
9.8K
Radical Substitution: Hydrogenolysis of Alkyl Halides with Tributyltin Hydride
2.3K
Radical substitution reactions can be used to remove functional groups from molecules. The hydrogenolysis of alkyl halides is one such reaction, where the weak Sn–H bond in tributyltin hydride reacts with alkyl halides to form alkanes. Here, the reagent Bu3SnH yields tributyltin halide as a byproduct.
The bonds formed in this reaction are stronger than the bonds broken, making it energetically favorable. The reaction follows a radical chain mechanism similar to radical halogenation reactions,...
The bonds formed in this reaction are stronger than the bonds broken, making it energetically favorable. The reaction follows a radical chain mechanism similar to radical halogenation reactions,...
2.3K
Alkyl Halides
19.6K
Structural Properties
Alkyl halides are halogen-substituted alkanes wherein one or more hydrogen atoms of an alkane is replaced by a halogen atom such as fluorine, chlorine, bromine, or iodine. The carbon atom in an alkyl halide is bonded to the halogen atom, which is sp3-hybridized and exhibits a tetrahedral shape.
Unlike alkyl halides, compounds in which a halogen atom is bonded to an sp2 -hybridized carbon atom of a carbon-carbon double bond (C=C) are called vinyl halides. Whereas aryl...
Alkyl halides are halogen-substituted alkanes wherein one or more hydrogen atoms of an alkane is replaced by a halogen atom such as fluorine, chlorine, bromine, or iodine. The carbon atom in an alkyl halide is bonded to the halogen atom, which is sp3-hybridized and exhibits a tetrahedral shape.
Unlike alkyl halides, compounds in which a halogen atom is bonded to an sp2 -hybridized carbon atom of a carbon-carbon double bond (C=C) are called vinyl halides. Whereas aryl...
19.6K
Radical Reactivity: Nucleophilic Radicals
2.6K
Radicals adjacent to electron-donating groups are called nucleophilic radicals. These radicals readily react with electrophilic alkenes. The SOMO–LUMO interactions are the driving force for the reaction, where the high-energy SOMO of the electron-rich, nucleophilic radicals interacts with the low-energy LUMO of the electron-deficient, electrophilic alkenes. Such SOMO–LUMO interactions are the basis of reactive radical traps, affecting the selectivity in radical reactions. For...
2.6K
Radical Reactivity: Electrophilic Radicals
2.4K
Radicals adjacent to electron‐withdrawing groups are called electrophilic radicals. These radicals readily react with nucleophilic alkenes. For example, the malonate radical, in which the radical center is flanked by two electron‐withdrawing groups, reacts readily with butyl vinyl ether, which consists of an electron‐donating oxygen substituent. The reaction between electrophilic malonate radical and nucleophilic vinyl ether is favored because the radical has a...
2.4K
Preparation of Alkynes: Alkylation Reaction
12.0K
Introduction
Alkylation of terminal alkynes with primary alkyl halides in the presence of a strong base like sodium amide is one of the common methods for the synthesis of longer carbon-chain alkynes. For example, treatment of 1-propyne with sodium amide followed by reaction with ethyl bromide yields 2-pentyne.
Alkylation of terminal alkynes with primary alkyl halides in the presence of a strong base like sodium amide is one of the common methods for the synthesis of longer carbon-chain alkynes. For example, treatment of 1-propyne with sodium amide followed by reaction with ethyl bromide yields 2-pentyne.
12.0K


