直接催化抗马尔科夫尼科夫的添加碳酸酸基因
Andrew J Perkowski1, David A Nicewicz
1Department of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill, North Carolina 27599-3290, United States.
Journal of the American Chemical Society
|July 2, 2013
概括
这项研究引入了直接的催化抗马尔科夫尼科夫添加碳酸酸基因使用福祖米酸光氧化剂. 这种方法有效地从各种烯酸和碳酸酸中合成抗马尔科夫尼科夫添加剂.
科学领域:
- 有机化学 有机化学
- 催化剂是一种催化剂.
- 摄影化学的使用.
背景情况:
- 直接添加碳酸酸是一种有价值的转化.
- 现有的方法往往缺乏选择性或需要苛刻的条件.
- 开发催化和选择性方法对于合成效率至关重要.
研究的目的:
- 报告一种新型的直接催化抗马尔科夫尼科夫添加碳酸酸到基的新型催化剂.
- 建立一种适用于各种基板的多功能方法.
- 为了研究反应机制.
主要方法:
- 使用福祖米酸光氧化剂作为催化剂.
- 采用原子供体的亚基显量量.
- 将各种可氧化烯 (烯,三替代烯,胺) 与碳素酸反应.
主要成果:
- 独家形成反马尔科夫尼科夫的附加引证.
- 对一系列烯酸和碳酸酸的成功应用.
- 标记实验提供了机械学的见解.
结论:
- 已经实现了对烯的直接催化抗马尔科夫尼科夫添加碳酸酸的方法.
- 开发的方法提供了高选择性和广泛的基质范围.
- 催化系统展示了有效合成有价值有机化合物的潜力.
相关概念视频
Radical Anti-Markovnikov Addition to Alkenes: Overview
The addition of hydrogen bromide to alkenes in the presence of hydroperoxides or peroxides proceeds via an anti-Markovnikov pathway and yields alkyl bromides.
Radical Anti-Markovnikov Addition to Alkenes: Mechanism
The reaction of hydrogen bromide with alkenes in the presence of hydroperoxides or peroxides proceeds via anti-Markovnikov addition. The radical chain reaction comprises initiation, propagation, and termination steps.
The mechanism starts with chain initiation, which involves two steps. In the first chain initiation step, a weak peroxide bond is homolytically cleaved upon mild heating to form two alkoxy radicals. In the second initiation step, a hydrogen atom is abstracted by the alkoxy radical...
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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.
Regioselectivity of Electrophilic Additions to Alkenes: Markovnikov's Rule
If a set of reactants can yield multiple constitutional isomers, but one of the isomers is obtained as the major product, the reaction is said to be regioselective. In such reactions, bond formation or breaking is favored at one reaction site over others.
The hydrohalogenation of an unsymmetrical alkene can yield two haloalkane products, depending on which vinylic carbon takes up the halogen. However, one product usually predominates, where hydrogen adds to the vinylic carbon bearing the...
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Acid-Catalyzed Aldol Addition Reaction
The aldol reaction of a ketone under acidic conditions successfully forms an unsaturated carbonyl as the final product instead of an aldol. The acid-catalyzed aldol reaction is depicted in Figure 1.
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.

