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Updated: Jun 13, 2026

08:43
Protocol for the Synthesis of Ortho-trifluoromethoxylated Aniline Derivatives
Published on: January 19, 2016
末端アルキンがMe3SiCF3で銅媒介型エアロビック酸化トリフルオロメチル化される
1Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Lu, Shanghai 200032, China.
Journal of the American Chemical Society
|May 11, 2010
まとめ
新しい銅触媒反応は,簡単に入手可能な試薬を使用して,トリフローロメチル基を端末アルキンに効率的に添加します. この方法は,トリフローロメチル化アセチレンを合成するための様々な機能群を許容し,多用途です.
科学分野:
- 有機化学 オーガニック・ケミストリー
- 有機金属化学 有機金属化学
背景:
- トリフローロメチル化化合物は,医薬品と材料科学において極めて重要です.
- トライフルオロメチル基を導入するための効率的な方法を開発することは非常に望ましい.
研究 の 目的:
- 端末アルキンの銅媒介型トリフルオロメチル化の効率的な開発.
- トライフルオロメチル化アセチレンを合成するための一般的かつ実用的な方法の確立.
主な方法:
- 核愛型トリフルオロメチル化反応剤であるトリメチル・トリフルオロメチルシラン (Me3SiCF3) を用いた銅媒介反応.
- アロマティック・ターミナル・アルキンとアリファティック・ターミナル・アルキンを基底として利用した.
主要な成果:
- 末端アルキンの効率的なトリフローロメチル化が成功しました.
- アミノ, -OMe, -CO2Et, -Br, -NO2.2を含む多様な機能群に対する耐性が実証されています.
- 得られたトリフローロメチル化アセチレンは,高収量と高純度である.
結論:
- 開発された銅媒介反応は,一般的で,単純で,実用的に有用な方法である.
- このプロトコルは,トリフローロメチル化アセチレンの合成のための貴重なツールを提供します.
関連する概念動画
Alkenes via Reductive Coupling of Aldehydes or Ketones: McMurry Reaction
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Oxymercuration–reduction of alkenes is one of the major reactions converting alkenes to alcohols. It involves the hydration of alkenes with mercuric acetate in a mixture of tetrahydrofuran and water, forming an organomercury adduct. This is followed by a demercuration step in which the adduct is reduced to an alcohol using sodium borohydride.
Preparation and Reactions of Sulfides
Sulfides are the sulfur analog of ethers, just as thiols are the sulfur analog of alcohol. Like ethers, sulfides also consist of two hydrocarbon groups bonded to the central sulfur atom. Depending upon the type of groups present, sulfides can be symmetrical or asymmetrical. Symmetrical sulfides can be prepared via an SN2 reaction between 2 equivalents of an alkyl halide and one equivalent of sodium sulfide.
Oxidation of Alkenes: Syn Dihydroxylation with Osmium Tetraoxide
Alkenes are converted to 1,2-diols or glycols through a process called dihydroxylation. It involves the addition of two hydroxyl groups across the double bond with two different stereochemical approaches, namely anti and syn. Dihydroxylation using osmium tetroxide progresses with syn stereochemistry.
Alkynes to Carboxylic Acids: Oxidative Cleavage
Alkynes undergo oxidative cleavage in the presence of oxidizing reagents like potassium permanganate and ozone. The triple bond — one σ bond and two π bonds — is completely cleaved, and the alkyne is oxidized to carboxylic acids. When warm and basic aqueous potassium permanganate is used as an oxidizing agent, alkynes are first converted to carboxylate salts via an unstable α-diketone intermediate. Further, a mild acid treatment protonates the carboxylate anions generating free carboxylic acid...
Acid Halides to Ketones: Gilman Reagent
Lithium dialkyl cuprate, also known as Gilman reagents, selectively reduces acid halides to ketones. The acid chloride is treated with Gilman reagent at −78 °C in the presence of ether solution to produce a ketone in good yield.
As shown below, the mechanism proceeds in two steps. First, one of the alkyl groups of the reagent acts as a nucleophile and attacks the acyl carbon of the acid chloride to form a tetrahedral intermediate. This is followed by the reformation of the carbon–oxygen double...
As shown below, the mechanism proceeds in two steps. First, one of the alkyl groups of the reagent acts as a nucleophile and attacks the acyl carbon of the acid chloride to form a tetrahedral intermediate. This is followed by the reformation of the carbon–oxygen double...
