δ-C-H アルコールの単体および二酸化
Alastair N Herron1, Dongxin Liu1, Guoqin Xia1
1Department of Chemistry , The Scripps Research Institute , 10550 North Torrey Pines Road , La Jolla , California 92037 , United States.
Journal of the American Chemical Society
|January 31, 2020
まとめ
遠隔C-H機能化のためのアルコキシラジカルを生成する新しい前駆体. この方法により,軽度で選択的な化と塩化が可能になり,複雑な二酸化物構造へのアクセスを可能にします.
科学分野:
- 有機化学
- 合成方法論
- ラジカル・ケミストリー
背景:
- アルコキシラジカルは,1,5-水素原子抽象化による遠隔C-H機能化を容易にする.
- 伝統的な生成方法は,硬い酸化物質,紫外線,または過酸化物を含み,合成アプリケーションを制限します.
研究 の 目的:
- アルコキシラジカルを生成する 新しく穏やかで効率的な方法を開発する
- 選択的なリモートC-Hハロゲネーションを可能にするため,新しい根幹の前駆体を使用します.
主な方法:
- ベンチに安定した前駆体が合成され,特徴づけられました.
- 先駆体は単電子酸化経路で分解してアルコキシラジカルを生成する.
- 遠隔C-H化および塩化反応は軽度な条件下で実施された.
主要な成果:
- アルコキシラジカルへの軽い経路を提供する.
- 高度に選択的な遠隔C-Hモノハロゲネーションが達成されました.
- 繰り返しハロゲン化により,遠隔ダイハリドモチーフ (CF2,CFC1) の合成が可能になった.
結論:
- 遠隔C-H機能化のための汎用性のあるプラットフォームを提供します.
- この方法は,伝統的なアルコキシラジカル生成の限界を克服します.
- 有効なハロゲン化合物の 簡単な合成を可能にします
関連する概念動画
Acid-Catalyzed α-Halogenation of Aldehydes and Ketones
4.7K
By replacing an α-hydrogen with a halogen, acid-catalyzed α-halogenation of aldehydes or ketones yields a monohalogenated product
In the first step of the mechanism, the acid protonates the carbonyl oxygen resulting in a resonance-stabilized cation, which subsequently loses an α-hydrogen to form an enol tautomer. The C=C bond in an enol is highly nucleophilic because of the electron-donating nature of the –OH group. Consequently, the double bond attacks an electrophilic halogen to form a...
In the first step of the mechanism, the acid protonates the carbonyl oxygen resulting in a resonance-stabilized cation, which subsequently loses an α-hydrogen to form an enol tautomer. The C=C bond in an enol is highly nucleophilic because of the electron-donating nature of the –OH group. Consequently, the double bond attacks an electrophilic halogen to form a...
4.7K
Halogenation of Alkenes
18.2K
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.
18.2K
Base-Promoted α-Halogenation of Aldehydes and Ketones
4.1K
α-Halogenation of aldehydes and ketones is a reaction involving the substitution of α hydrogens with halogens in the presence of a base. The reaction begins with the abstraction of α hydrogen by the base to produce a nucleophilic enolate ion. This intermediate undergoes a subsequent nucleophilic substitution with the halogen to produce a monohalogenated carbonyl compound. If the starting substrate has more than one α hydrogen, it is difficult to stop the reaction...
4.1K
Electrophilic Addition to Alkynes: Hydrohalogenation
11.2K
Electrophilic addition of hydrogen halides, HX (X = Cl, Br or I) to alkenes forms alkyl halides as per Markovnikov's rule, where the hydrogen gets added to the less substituted carbon of the double bond. Hydrohalogenation of alkynes takes place in a similar manner, with the first addition of HX forming a vinyl halide and the second giving a geminal dihalide.
11.2K
Formation of Halohydrin from Alkenes
14.5K
An alkene, such as propene, reacts with bromine in the presence of water to yield a halohydrin. Halohydrins contain a halogen and a hydroxyl group attached to adjacent carbons. When the halogen is bromine, it is called a bromohydrin, while a chlorohydrin has chlorine as the halogen.
14.5K
Electrophilic 1,2- and 1,4-Addition of X2 to 1,3-Butadiene
3.3K
Electrophilic addition of halogens to alkenes proceeds via a cyclic halonium ion to form a 1,2-dihalide or a vicinal dihalide.
3.3K


