在温和的条件下,胺乙烯酸盐的帕拉催化分子间α-arylation
Takuo Hama1, Darcy A Culkin, John F Hartwig
1Department of Chemistry, Yale University, P.O. Box 208107, New Haven, Connecticut 06520-8107, USA.
Journal of the American Chemical Society
|April 13, 2006
概括
这项研究引入了使用乙酸盐的化催化阿尔法-化和化的化. 这种方法为合成功能化胺提供了一种多用途的方法,扩大了有机化学中的合成可能性.
科学领域:
- 有机化学 有机化学
- 催化剂是一种催化剂.
- 合成方法论 合成方法论
背景情况:
- 催化交叉合反应在有机合成中至关重要.
- 胺功能化对于开发药品和材料至关重要.
- 之前的胺结法方法在范围和条件上有局限性.
研究的目的:
- 开发一种新的催化方法,用于胺的分子间α-arylation和vinylation.
- 探索乙烯酸盐在胺合反应中的应用.
- 扩大胺功能化的基质范围和效率.
主要方法:
- 使用的催化剂,包括含有Q-或二维Pd (I) 复合物的催化剂.
- 采用了三种不同类型的乙烯酸,这些乙烯酸来自胺基.
- 在不同的反应条件下,与乙烯酸结合的烯和乙烯基化物.
主要成果:
- 在使用各种乙烯酸盐对胺的α-arylation和vinylation中取得了高产量.
- 在甲烯和皮里丁上与广泛的功能群的兼容性得到了证明.
- 成功地将该方法应用于吗胺,产生和化物的前体.
结论:
- 与金属酸盐相比,开发的乙烯酸盐方法显著扩大了胺结的范围.
- 在温和条件下 (室温至70°C) 反应有效地进行.
- 这种方法为合成复杂的胺衍生物提供了有价值的工具.
相关概念视频
Acidity of 1-Alkynes
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.
α-Halogenation of Carboxylic Acid Derivatives: Overview
Unlike aldehydes and ketones, carboxylic acids do not readily participate in α halogenation reactions via enols or enolate intermediates. However, α-halogenated acids are obtained through other methods. One of the approaches is the Hell–Volhard–Zelinsky (HVZ) reaction, wherein the carboxylic acid is treated with halogen in the presence of PBr3. It involves the conversion of acid to acid halide, which exists in equilibrium with its enol form. The enol attacks the electrophilic halogen to produce...
Acid Halides to Esters: Alcoholysis
Alcoholysis is a nucleophilic acyl substitution reaction in which an alcohol functions as a nucleophile. Acid halides react with alcohol to produce esters. The mechanism proceeds in three steps:
Acid-Catalyzed α-Halogenation of Aldehydes and Ketones
By replacing an α-hydrogen with a halogen, acid-catalyzed α-halogenation of aldehydes or ketones yields a monohalogenated product
In the first step of the mechanism, the acid protonates the carbonyl oxygen resulting in a resonance-stabilized cation, which subsequently loses an α-hydrogen to form an enol tautomer. The C=C bond in an enol is highly nucleophilic because of the electron-donating nature of the –OH group. Consequently, the double bond attacks an electrophilic halogen to form a...
In the first step of the mechanism, the acid protonates the carbonyl oxygen resulting in a resonance-stabilized cation, which subsequently loses an α-hydrogen to form an enol tautomer. The C=C bond in an enol is highly nucleophilic because of the electron-donating nature of the –OH group. Consequently, the double bond attacks an electrophilic halogen to form a...
α-Bromination of Carboxylic Acids: Hell–Volhard–Zelinski Reaction
The method to achieve α-brominated carboxylic acids using a mixture of phosphorus tribromide and bromine is known as the Hell–Volhard–Zelinski reaction. The reaction is catalyzed by phosphorus tribromide, which can be used directly or produced in situ from red phosphorus and bromine. The mechanism comprises PBr3 catalyzed conversion of acid to acid bromide and hydrogen bromide. The acid bromide enolizes to its enol form in the presence of HBr. The nucleophilic enol attacks the bromine molecule...
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.


