非常实用的铜 (I) /TEMPO催化剂系统用于初级醇的化学选择性有氧氧化
Jessica M Hoover1, Shannon S Stahl
1Department of Chemistry, University of Wisconsin-Madison, 1101 University Ave, Madison, Wisconsin 53706, USA.
Journal of the American Chemical Society
|August 25, 2011
概括
这项研究引入了一种新的铜 (I) /TEMPO催化剂,用于使用环境空气有效地将初级酒精氧化为化物. 这种方法为有机合成提供了一种更绿色,更实用的方法.
科学领域:
- 有机化学 有机化学
- 催化剂是一种催化剂.
- 绿色化学 绿色化学
背景情况:
- 有氧氧化非常重要,但受到范围和实际问题 (如纯氧化二氧化碳) 的限制.
- 现有的方法往往需要复杂的催化剂或恶劣的条件,阻碍了广泛采用.
研究的目的:
- 开发一种高效和有选择性的催化剂系统,用于使初级酒精氧化为化物.
- 在温和条件下利用环境空气作为氧化剂.
主要方法:
- 使用了一种新的 (bpy) Cu(I) /TEMPO催化剂系统.
- 在室温下进行反应,使用环境空气作为氧化剂.
主要成果:
- 催化剂系统有效氧化了广泛的初级酒精 (基,基,基) 到化物.
- 对初级酒精的高选择性允许对未受保护的二醇进行选择性氧化.
- 证明了与各种功能组的兼容性.
结论:
- 开发的催化剂系统为有氧酒精氧化提供了一种实用和选择性的方法.
- 这一进步为有机化学中的化物合成提供了一个更绿色的替代方案.
更多相关视频
相关概念视频
Oxidation 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:
Oxidation 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.
Alkynes to Aldehydes and Ketones: Hydroboration-Oxidation
Introduction
One of the convenient methods for the preparation of aldehydes and ketones is via hydration of alkynes. Hydroboration-oxidation of alkynes is an indirect hydration reaction in which an alkyne is treated with borane followed by oxidation with alkaline peroxide to form an enol that rapidly converts into an aldehyde or a ketone. Terminal alkynes form aldehydes, whereas internal alkynes give ketones as the final product.
One of the convenient methods for the preparation of aldehydes and ketones is via hydration of alkynes. Hydroboration-oxidation of alkynes is an indirect hydration reaction in which an alkyne is treated with borane followed by oxidation with alkaline peroxide to form an enol that rapidly converts into an aldehyde or a ketone. Terminal alkynes form aldehydes, whereas internal alkynes give ketones as the final product.
Radical 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...
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.
Oxidation 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.
![[(DPEPhos)(bcp)Cu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F59739.jpg&w=3840&q=50)

