电化学有氧瓦克尔型氧化三基替代基到1,2,2-三基乙
Zhou Zhang1, Jin Li2, Zhiwei Cai3
1School of Chemical Engineering & Technology, China University of Mining and Technology, Xuzhou 221116, Jiangsu, P. R. China. zhaofy@cumt.edu.cn.
概括
一种新的电化学方法利用氧气从基中合成三烯乙. 这种无过渡金属的瓦克尔型氧化是三替代基的首次氧化,提供温和的条件和良好的产量.
科学领域:
- 有机化学 有机化学
- 电化学 电化学 电化学
- 合成方法论 合成方法论
背景情况:
- 瓦克尔氧化是基功能化的基石.
- 将瓦克尔型反应扩展到固态阻碍的三替代基仍然具有挑战性.
- 开发无过渡金属的合成路径是非常可取的.
研究的目的:
- 开发一种有效的电化学瓦克尔型氧化方法,用于合成1,2,2-三甲.
- 为了扩大瓦克尔型氧化物的基质范围,将其扩展到三替代基.
- 建立一种无过渡金属,温和和功能组耐受性的合成方法.
主要方法:
- 三基替代基的电化学氧化.
- 使用分子氧气 (O2) 作为唯一的氧气来源.
- 在没有过渡金属催化剂的情况下在温和条件下进行反应.
主要成果:
- 成功合成了各种1,2,2-三甲的合成.
- 首次证明了三替代基的瓦克尔型氧化.
- 取得了令人满意的产量,具有高度的功能组兼容性.
- 机理学研究表明,C=O键通过阴离子中间体和超氧化基形成.
结论:
- 已经建立了一个高效和新的电化学瓦克尔型氧化方法.
- 这种方法提供了一种多功能,无金属的通道到有价值的三甲基乙化合物.
- 这些发现扩大了瓦克尔型氧化对挑战性基质的实用性.
相关概念视频
Oxidative Cleavage of Alkenes: Ozonolysis
10.4K
In ozonolysis, ozone is used to cleave a carbon–carbon double bond to form aldehydes and ketones, or carboxylic acids, depending on the work-up.
Ozone is a symmetrical bent molecule stabilized by a resonance structure.
Ozone is a symmetrical bent molecule stabilized by a resonance structure.
10.4K
Oxidation of Alkenes: Syn Dihydroxylation with Osmium Tetraoxide
10.2K
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.
10.2K
Oxymercuration-Reduction of Alkenes
7.5K
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.
7.5K
Oxidation of Alkenes: Anti Dihydroxylation with Peroxy Acids
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Diols are compounds with two hydroxyl groups. In addition to syn dihydroxylation, diols can also be synthesized through the process of anti dihydroxylation. The process involves treating an alkene with a peroxycarboxylic acid to form an epoxide. Epoxides are highly strained three-membered rings with oxygen and two carbons occupying the corners of an equilateral triangle. This step is followed by ring-opening of the epoxide in the presence of an aqueous acid to give a trans diol.
5.8K
Oxidation of Alkenes: Syn Dihydroxylation with Potassium Permanganate
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Alkenes can be dihydroxylated using potassium permanganate. The method encompasses the reaction of an alkene with a cold, dilute solution of potassium permanganate under basic conditions to form a cis-diol along with a brown precipitate of manganese dioxide.
11.5K
Reactions of Aldehydes and Ketones: Baeyer–Villiger Oxidation
4.1K
Baeyer–Villiger oxidation converts aldehydes to carboxylic acids and ketones to esters. The reaction uses peroxy acids or peracids and is often catalyzed by acid. The reaction is named after its pioneers, Adolf von Baeyer and Victor Villiger. The reaction is achieved by a wide range of peracids such as m-chloroperoxybenzoic acid (mCPBA), perbenzoic acid (C6H5COOOH), peracetic acid (CH3COOOH), hydrogen peroxide (H2O2), and tert-butyl hydroperoxide (t-BuOOH).
The carbonyl center is...
The carbonyl center is...
4.1K


