水溶液中のアルキル基のトリフローロメチル化
Haigen Shen1, Zhonglin Liu1, Pei Zhang1
1Key Laboratory of Organofluorine Chemistry and Collaborative Innovation Center of Chemistry for Life Sciences, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences , 345 Lingling Road, Shanghai 200032, China.
Journal of the American Chemical Society
|July 11, 2017
まとめ
新規のBPyCu ((CF3) 3反応剤を用いた,銅触媒によるアルキルハリドのトリフローロメチル化が効率的である. この方法は,軽度の条件下でトリフローロメチル化化合物への汎用的な経路を提供します.
科学分野:
- 有機化学
- 有機金属化学
- ラジカル・ケミストリー
背景:
- トリフローロメチル群は 医薬品や材料において極めて重要です
- トリフローロメチル化のための効率的な方法の開発は,継続的な課題です.
- 銅の触媒は,C-CF3結合形成の有望な経路を提供します.
研究 の 目的:
- アルキル基のトリフローロメチル化のための新しい銅媒介法を開発する.
- 開発されたプロトコルの範囲と限界を探求する.
- 反応のメカニズムを解明する
主な方法:
- BPyCu ((CF3)3) とアルキルハリドの銅触媒反応.
- トライエチルシラン (Et3SiH) とポータシウムパースルファート (K2S2O8) を使って急激反応を開始する.
- 室温でアセトンで反応する.
主要な成果:
- 各種の原発および二次アルキルハリドのトリフローロメチル化に成功した.
- トリフローロメチル化製品から得られた良い収穫量.
- 幅広い機能群の互換性を示した.
- Cu (II) -CF3の中間物質を含むメカニズムを提案した.
結論:
- アルキルハリドのための新しい効率的な銅媒介型トリフローロメチル化プロトコルが確立されています.
- この方法は多用途で,スケーラブルで,幅広い機能群の許容性を示しています.
- この発見は,トリフローロメチル基を導入するための合成方法の進歩に寄与する.
関連する概念動画
Radical Substitution: Halogenation of Alkanes and Alkyl Substituents
10.4K
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...
10.4K
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
Hydroboration-Oxidation of Alkenes
12.0K
In addition to the oxymercuration–demercuration method, which converts the alkenes to alcohols with Markovnikov orientation, a complementary hydroboration-oxidation method yields the anti-Markovnikov product. The hydroboration reaction, discovered in 1959 by H.C. Brown, involves the addition of a B–H bond of borane to an alkene giving an organoborane intermediate. The oxidation of this intermediate with basic hydrogen peroxide forms an alcohol.
12.0K
Radical Substitution: Allylic Chlorination
3.4K
Typically, when alkenes react with halogens at low temperatures, an addition reaction occurs. However, upon increasing the temperature or under reaction conditions that form radicals, providing a low but steady concentration of halogen radicals, allylic substitution reaction is favored. This is because allylic hydrogens are very reactive as the formed intermediate is resonance stabilized. For example, when propene is treated with chlorine in the gas phase at 400 °C, it undergoes allylic...
3.4K
Alkyl Halides
21.0K
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...
21.0K
Halogenation of Alkenes
20.7K
Halogenation is the addition of chlorine or bromine across the double bond in an alkene to yield a vicinal dihalide. The reaction occurs in the presence of inert and non-nucleophilic solvents, such as methylene chloride, chloroform, or carbon tetrachloride.
Consider the bromination of cyclopentene. Molecular bromine is polarized in the proximity of the π electrons of cyclopentene. An electrophilic bromine atom adds across the double bond, forming a cyclic bromonium ion intermediate.
Consider the bromination of cyclopentene. Molecular bromine is polarized in the proximity of the π electrons of cyclopentene. An electrophilic bromine atom adds across the double bond, forming a cyclic bromonium ion intermediate.
20.7K


