集成的电化学化学氧化,由氧硫离子介导
Yosuke Ashikari1, Toshiki Nokami, Jun-ichi Yoshida
1Department of Synthetic Chemistry and Biological Chemistry, Graduate School of Engineering, Kyoto University, Kyoto 615-8510, Japan.
Journal of the American Chemical Society
|July 13, 2011
概括
本研究介绍了一种使用二甲基硫氧化物 (DMSO) 的电化学化学氧化方法,将碳酸转化为碳化合物. 这种新的方法有效地氧化各种有机基质,包括二甲基甲和基甲,变成有价值的和化物.
科学领域:
- 有机化学 有机化学
- 电化学 电化学 电化学
- 氧化反应 氧化反应
背景情况:
- 碳酸是有机合成中的关键中间体.
- 氧化反应对于转化有机分子至关重要.
- 甲基二硫氧化物 (DMSO) 是有机化学中的一个多用途的试剂.
研究的目的:
- 开发一种集成的电化学化学氧化方法.
- 为了利用carbocations和DMSO合成碳化合物.
- 探索这种方法在各种有机转化中的应用.
主要方法:
- 通过"池"方法或电化学方法生成碳酸.
- 在现场用二甲基硫氧化物 (DMSO) 捕获碳酸盐,以形成氧硫离子.
- 使用三乙烯将氧硫离子转化为碳化合物.
主要成果:
- 从碳酸盐和DMSO中成功合成了氧硫离子.
- 证明了氧硫离子转化为碳化合物.
- 应用该方法将二甲基甲氧化为二甲基,二甲基氧化为二甲基,二甲基氧化为二甲基,二甲基替代氧化为1,2-二甲基.
- 从含有核友基的不和基质中获得循环化碳烯化合物.
结论:
- 集成的电化学-化学氧化提供了一条有效的路径到碳化合物.
- 这种方法为氧化各种有机基质提供了一种多功能策略.
- 该方法适用于非循环和循环碳化合物合成.
相关概念视频
02:37Oxidation of Alcohols
In this lesson, the oxidation of alcohols is discussed in depth. The various reagents used for oxidation of primary and secondary alcohols are detailed, and their mechanism of action is provided.
The process of oxidation in a chemical reaction is observed in any of the three forms:
The process of oxidation in a chemical reaction is observed in any of the three forms:
01:46Oxidative Cleavage of Alkenes: Ozonolysis
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.
01:21Radical Oxidation of Allylic and Benzylic Alcohols
Activated manganese(IV) oxide can selectively oxidize allylic and benzylic alcohols via a radical intermediate mechanism. Primary allylic alcohols are oxidized to aldehydes, while secondary allylic alcohols yield ketones. The redox reaction of potassium permanganate with an Mn(II) salt such as manganese sulfate (under either alkaline or acidic conditions), followed by thorough drying, yields the oxidizing agent: activated MnO2. While MnO2 is insoluble in the solvents used for the reaction, the...
02:04Oxidation of Alkenes: Anti Dihydroxylation with Peroxy Acids
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.
02:44Oxidation 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.
02:21Oxidation of Alkenes: Syn Dihydroxylation with Potassium Permanganate
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.