释放易斯酸度通过氧化非无罪的氨酸替代的氨酸
Taylor P L Cosby1, Avik Bhattacharjee1, Samantha K Henneberry1
1Department of Chemistry, York University, 4700 Keele Street, Toronto, ON, M3J 1P3, Canada. caputo@yorku.ca.
概括
研究人员开发了一种新的方法,通过氧化酸来提高易斯酸度. 这就产生了稳定的基离子,显著提高了催化活性,使得较少反应性的在化学反应中更有用.
科学领域:
- 有机金属化学 有机金属化学
- 催化剂是一种催化剂.
- 激进化学 激进化学是什么
背景情况:
- 易斯酸是有机合成中的关键催化剂.
- 子是常见的易斯酸,但可以通过它们的反应性来限制.
- 提高易斯酸度是扩大其催化应用的关键.
研究的目的:
- 引入一种新的策略,以提高玻酸的易斯酸度.
- 为了研究氧化物种的形成和特性.
- 通过使用新方法来证明改进的催化性能.
主要方法:
- 一个的单电子氧化,具有一个悬挂的提亚组.
- 计算研究 (例如,DFT) 来分析电子结构和反应性.
- 对增强的易斯酸度和催化活性进行实验验证.
主要成果:
- 从氧化中形成一个持久的基离子.
- 与中性相比,激素的易斯酸度和电友性显著增加.
- 在使用氧化物种的反应中观察到增强的催化活性.
结论:
- 单电子氧化是一种可行的方法来激活和增强相对惰性的酸的易斯酸度.
- 持久基离子中间体表现出优越的电友性和催化潜力.
- 这种方法为设计强大的易斯酸催化剂提供了新的途径.
相关概念视频
Hydroboration-Oxidation of Alkenes
8.1K
In addition to the oxymercuration–demercuration method, which converts the alkenes to alcohols with Markovnikov orientation, a complementary hydroboration-oxidation method yields the anti-Markovnikov product. The hydroboration reaction, discovered in 1959 by H.C. Brown, involves the addition of a B–H bond of borane to an alkene giving an organoborane intermediate. The oxidation of this intermediate with basic hydrogen peroxide forms an alcohol.
8.1K
Electrophilic Aromatic Substitution: Chlorination and Bromination of Benzene
8.1K
Chlorination and bromination are important classes of electrophilic aromatic substitutions, where benzene reacts with chlorine or bromine in the presence of a Lewis acid catalyst to give halogenated substitution products. A Lewis acid such as aluminium chloride or ferric chloride catalyzes the chlorination, and ferric bromide catalyzes the bromination reactions. During the bromination of alkenes, bromine polarizes and becomes electrophilic. However, in the bromination of benzene, the bromine...
8.1K
Lewis Acids and Bases
14.1K
This lesson delves into Lewis acids and bases in the context of the octet rule for electron-deficient compounds. Here, the concept is discussed, emphasizing the group 13 elements like boron or aluminium. Since group 13 elements possess three valence electrons, they form trivalent compounds with a sextet of electrons and a vacant orbital for the central atom. Consequently, these electron-deficient compounds accept electrons from other species to complete their octet in a chemical reaction. They...
14.1K
Electrophilic Aromatic Substitution: Fluorination and Iodination of Benzene
6.0K
Bromination and chlorination of aromatic rings by electrophilic aromatic substitution reactions are easily achieved, but fluorination and iodination are difficult to achieve. Fluorine is so reactive that its reaction with benzene is difficult to control, resulting in poor yields of monofluoroaromatic products. To address this, Selectfluor reagent is used as a fluorine source in which a fluorine atom is bonded to a positively charged nitrogen.
6.0K
Alkynes to Aldehydes and Ketones: Hydroboration-Oxidation
18.0K
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.
18.0K
Regioselectivity and Stereochemistry of Hydroboration
8.1K
A significant aspect of hydroboration–oxidation is the regio- and stereochemical outcome of the reaction.
Hydroboration proceeds in a concerted fashion with the attack of borane on the π bond, giving a cyclic four-centered transition state. The –BH2 group is bonded to the less substituted carbon and –H to the more substituted carbon. The concerted nature requires the simultaneous addition of –H and –BH2 across the same face of the alkene giving syn...
Hydroboration proceeds in a concerted fashion with the attack of borane on the π bond, giving a cyclic four-centered transition state. The –BH2 group is bonded to the less substituted carbon and –H to the more substituted carbon. The concerted nature requires the simultaneous addition of –H and –BH2 across the same face of the alkene giving syn...
8.1K


