功能化子的非对称的直接阿尔多尔反应被基于双二胺的氨基有机催化剂催化
Jie Liu1, Zhigang Yang, Zhen Wang
1Key Laboratory of Green Chemistry & Technology, College of Chemistry, Sichuan University, Chengdu 610064, PR China.
Journal of the American Chemical Society
|April 3, 2008
概括
新的有机催化剂具有初级-二级胺,有效催化不对称的阿尔多尔反应. 这项研究产生了具有高效率和选择性的奇拉三级酒精,突出显示了质子化皮佩里丁的作用.
科学领域:
- 有机化学 有机化学
- 不对称的催化剂.
背景情况:
- 直接不对称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.
- 为阿尔多尔反应开发高效的有机催化剂仍然是一个重大挑战.
研究的目的:
- 设计和合成基于双素和氨基酸支架的新型有机催化剂.
- 研究这些新的有机催化剂在功能化子的非对称直接阿尔多尔反应中的催化活性.
主要方法:
- 初级-二级氨酸有机催化剂的合成.
- 使用功能化子 (α-keto酸盐,α-keto Ester,α,α-dialkoxy ketones) 的非对称的直接醇反应.
- 使用计算方法对反应过渡结构的理论研究.
主要成果:
- 有机催化剂成功催化了不对称的直接阿尔多尔反应.
- 基拉尔三级酒精产品的产量中等至高 (高达97%).
- 实现了高的异能选择活性 (高达98% ee).
结论:
- 设计的基于比斯皮丁和氨基酸的有机催化剂对不对称的阿尔多尔反应有效.
- 理论分析表明,质子化皮佩里丁在促进反应性和酶选择性方面起着至关重要的作用.
- 这项工作为合成性三级酒精提供了新的途径.
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相关概念视频
Aldol Condensation with β-Diesters: Knoevenagel Condensation
The Knoevenagel condensation is an aldol-type reaction involving the condensation of aldehydes or ketones with active methylene compounds such as β-diesters to produce substituted olefins.
Crossed Aldol Reaction Using Strong Bases: Directed Aldol Reaction
The reaction between two different carbonyl compounds comprising α hydrogen in the presence of a strong base like lithium diisopropylamide (LDA) to form a crossed aldol product is known as a directed aldol reaction. The directed aldol reaction is depicted in Figure 1.
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.
Intramolecular Aldol Reaction
Intramolecular aldol reaction occurs in dicarbonyl compounds such as dialdehydes, diketones, and keto-aldehydes. The dicarbonyl compounds possess more than one nucleophilic ⍺ carbon for the base to deprotonate and form the enolates. For example, in symmetrical diketones, there are four ⍺ carbons. Hence, four types of enolates are possible when treated with a base. However, since the molecule is symmetrical, the enolates formed on either side of one carbonyl group are equivalent to those formed...
α-Alkylation of Ketones via Enolate Ions
Ketones with α protons are deprotonated by strong bases like lithium diisopropylamide (LDA) to form enolate ions. The anion is stabilized by resonance, and its hybrid structure exhibits negative charges on the carbonyl oxygen and the α carbon. This ambident nucleophile can attack an electrophile via two possible sites: the carbonyl oxygen, known as O-attack, or the α carbon, known as C-attack. The nucleophilic attack via the carbanionic site is preferred. This is due to the strong interaction...
Base-Catalyzed Aldol Addition Reaction
As depicted in Figure 1, base-catalyzed aldol addition involves adding two carbonyl compounds in aqueous sodium hydroxide to form a β-hydroxy carbonyl compound.


