一种高效的有机催化剂,用于基与化物的直接阿尔多尔反应[已修正]
Zhuo Tang1, Zhi-Hua Yang, Xiao-Hua Chen
1Key Laboratory for Asymmetric Synthesis and Chirotechnology of Sichuan Province, Chengdu Institute of Organic Chemistry, Chinese Academy of Sciences, Chengdu, 610041, China.
Journal of the American Chemical Society
|June 23, 2005
概括
石化L-胺胺有效催化直接的阿尔多尔反应. 提取电子的组增强了催化剂的性能,从各种化物和化物中产生高度反选择性的β-基.
科学领域:
- 有机化学 有机化学
- 不对称的催化剂.
背景情况:
- 直接的阿尔多尔反应是有机合成中的一个关键的碳-碳键形成反应.
- 为不对称的阿尔多尔反应开发高效和选择性的催化剂仍然是一个重大挑战.
研究的目的:
- 合成和评估新型L-胺胺作为直接阿尔多尔反应的有机催化剂.
- 调查替代剂的电子性质对催化剂活性和酶选择性的影响.
主要方法:
- 从β-氨基醇中提取的奇拉L-胺胺的合成.
- 在4-甲和乙之间的直接阿尔多尔反应中对催化剂的评估.
- 用一系列的和测试催化剂的性能,包括环素和环素.
主要成果:
- 带有电子吸收组的L-胺胺体表现出优异的催化活性和酶选择性.
- 催化剂4g (2 mol %) 有效地促进了与乙和butanone的各种化物的阿尔多尔反应,达到96%至>99%的反体过量 (ee).
- 对抗阿尔多尔产品的高分选择性 (95/5) 被观察到与循环松,并获得了优异的enantioselectivity (93% ee) 循环松.
结论:
- 石化L-胺胺是直接阿尔多尔反应的有效器官催化剂.
- 替代物的电子性质显著影响着催化效率和立体选择性.
- 这些催化剂提供了一条有前途的途径,以高度化丰富的β-基.
相关概念视频
Catalysis
The presence of a catalyst affects the rate of a chemical reaction. A catalyst is a substance that can increase the reaction rate without being consumed during the process. A basic comprehension of a catalysts’ role during chemical reactions can be understood from the concept of reaction mechanisms and energy diagrams.
Preparation of Alkynes: Alkylation Reaction
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.
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.
Aldehydes and Ketones with Alcohols: Hemiacetal Formation
Similar to water, alcohols can add to the carbonyl carbon of the aldehydes and ketones. The addition of one molecule of alcohol to the carbonyl compound forms the hemiacetal or half acetal. As depicted below, in a hemiacetal, the carbon is directly linked to an OH and OR group.
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...
Catalysis
Catalysis influences the rate of chemical reactions by providing an alternative reaction pathway with lower activation energy. A catalyst speeds up a reaction, but it is not consumed during the process. The fundamental principle of catalysis is the ability of a catalyst to alter the reaction mechanism, often introducing a more efficient pathway than the uncatalyzed process.In a catalyzed reaction, the catalyst participates directly in the reaction mechanism. It interacts with reactants to form...


