P,N-协调化功能化素 (NYPhos):用于小核的选择性单化的一种配体平台
Julian Löffler1, Nicolas Kaiser1, Daniel Knyszek1
1Chair of Inorganic Chemistry II, Faculty of Chemistry and Biochemistry, Ruhr-University Bochum, Universitätsstr. 150, 44801, Bochum, Germany.
Angewandte Chemie (International ed. in English)
|June 20, 2024
概括
新的P,N-连接体 (NYPhos) 能够对像氨和胺这样的小核友的选择性催化合. 这一突破实现了高活性,即使在室温下具有挑战性的烯化物,也促进了有机合成.
科学领域:
- 有机化学 有机化学
- 催化剂是一种催化剂.
- 连接体设计 连接体设计
背景情况:
- 催化合反应至关重要,但面临的选择性挑战与小核友.
- 在这些反应中控制选择性的配体的开发是研究的一个重要领域.
研究的目的:
- 开发一种新的P,N-配体平台,称为NYPhos,用于选择性催化合反应.
- 为了解决选择性控制问题,将小核友与具有挑战性的基质结合起来.
主要方法:
- 一个多样化的库的合成与aminophosphonium组 (NYPhos) 的 ylide-functionalized 素连接体.
- 在催化合反应中对14个NYPhos配体的选.
- 在催化循环中参与的复合物的隔离和结构分析.
主要成果:
- 在室温下实现了高活性乙,和胺的选择性单化,包括在室温下化.
- 在温和条件下证明了氨和初级胺的成功合.
- 证实了P,N-协调模式对于选择性和N-捐赠体强度的可调性的必要性.
结论:
- NYPhos 配体为控制催化合反应的选择性提供了一个多功能平台.
- 开发的配体使具有挑战性的基质和晚期药物修饰的有效功能化成为可能.
- 这项工作为为未来的催化应用设计量身定制的P,N-连接体提供了基础.
相关概念视频
Nucleophilic Aromatic Substitution of Aryldiazonium Salts: Aromatic SN1
2.1K
Treating arylamines with nitrous acid gives aryldiazonium salts that are effective substrates in nucleophilic aromatic substitution reactions. The diazonio group in these salts can be easily displaced by different nucleophiles, yielding a wide variety of substituted benzenes. The leaving group departs as nitrogen gas, and this easy elimination is the driving force for the substitution reaction.
In the Sandmeyer reaction, for example, the diazonio group is replaced by a chloro, bromo,...
In the Sandmeyer reaction, for example, the diazonio group is replaced by a chloro, bromo,...
2.1K
Preparation of Alkynes: Alkylation Reaction
10.1K
Introduction
Alkylation of terminal alkynes with primary alkyl halides in the presence of a strong base like sodium amide is one of the common methods for the synthesis of longer carbon-chain alkynes. For example, treatment of 1-propyne with sodium amide followed by reaction with ethyl bromide yields 2-pentyne.
Alkylation of terminal alkynes with primary alkyl halides in the presence of a strong base like sodium amide is one of the common methods for the synthesis of longer carbon-chain alkynes. For example, treatment of 1-propyne with sodium amide followed by reaction with ethyl bromide yields 2-pentyne.
10.1K
Nucleophilic Aromatic Substitution: Elimination–Addition
4.0K
Simple aryl halides do not react with nucleophiles. However, nucleophilic aromatic substitutions can be forced under certain conditions, such as high temperatures or strong bases. The mechanism of substitution under such conditions involves the highly unstable and reactive benzyne intermediate. Benzyne contains equivalent carbon centers at both ends of the triple bond, each of which is equally susceptible to nucleophilic attack. This 50–50 distribution of products is...
4.0K
Nucleophilic Aromatic Substitution: Addition–Elimination (SNAr)
3.8K
Nucleophilic substitution in aromatic compounds is feasible in substrates bearing strong electron-withdrawing substituents positioned ortho or para to the leaving group. The reaction proceeds via two steps: the addition of the nucleophile and the elimination of the leaving group.
The reaction begins with an attack of the nucleophile on the carbon that holds the leaving group. This results in the delocalization of the π electrons over the ring carbons. The resonance interaction between...
The reaction begins with an attack of the nucleophile on the carbon that holds the leaving group. This results in the delocalization of the π electrons over the ring carbons. The resonance interaction between...
3.8K
Aldehydes and Ketones to Alkenes: Wittig Reaction Overview
7.6K
The Wittig reaction is the conversion of carbonyl compounds-aldehydes and ketones-to alkenes using phosphorus ylides, or the Wittig reagent. The reaction was pioneered by Prof. Georg Wittig, for which he was awarded the Nobel Prize in Chemistry.
7.6K
Acidity of 1-Alkynes
9.7K
The acidic strength of hydrocarbons follows the order: Alkynes > Alkenes > Alkanes. The strength of an acid is commonly expressed in units of pKa — the lower the pKa, the stronger the acid. Among the hydrocarbons, terminal alkynes have lower pKa values and are, therefore, more acidic. For example, the pKa values for ethane, ethene, and acetylene are 51, 44, and 25, respectively, as shown here.
9.7K


