脯氨酸催化的不对称羟醛缩合反应的改进与拓展

引用本文: 鲁鸿, 翟奕蝶, 成星星, 高钰佳, 魏青, 魏颢. 脯氨酸催化的不对称羟醛缩合反应的改进与拓展[J]. 大学化学, 2024, 39(5): 154-162. doi: 10.3866/PKU.DXHX202310074 shu

Citation: Hong Lu, Yidie Zhai, Xingxing Cheng, Yujia Gao, Qing Wei, Hao Wei. Advancements and Expansions in the Proline-Catalyzed Asymmetric Aldol Reaction[J]. University Chemistry, 2024, 39(5): 154-162. doi: 10.3866/PKU.DXHX202310074 shu

脯氨酸催化的不对称羟醛缩合反应的改进与拓展

西北大学化学与材料科学学院, 化学国家级实验教学示范中心, 西安 710127

摘要: “脯氨酸催化的不对称羟醛缩合反应”是展现“对映异构”概念的经典实验。然而，受限于反应物活性和实验设计，“非对映异构”和“外消旋化”等“立体化学”概念未能在实验中体现。为进一步增强实验教学与理论教学的支撑融合，让学生通过实验充分理解有机化学中“立体化学”章节内容，我们对该反应进行了改进和拓展：(1) 将常规的两组分反应升级到三组分，通过芳基醛向高活性醛亚胺的转化，快速构建含有非对映异构体的连续手性中心产物；(2) 设置相反构型催化剂对照实验，并通过相反构型产物混合物旋光度的测定，引入“外消旋化”概念；(3) 引入核磁共振技术测定非对映异构体比例，加深对“非对映异构”概念的认识。结果表明，该实验重复性好、时长合适，内容设计兼具探索性和创新性，有助于激发学生的科学精神和创新意识，培养学生进行创新性实验研究的能力。

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English

Advancements and Expansions in the Proline-Catalyzed Asymmetric Aldol Reaction

National Demonstration Center for Experiment Chemistry Education, College of Chemistry & Materials Science, Northwest University, Xi’an 710127, China
Received Date: 19 October 2023
Revised Date: 08 January 2024

Abstract: The proline-catalyzed asymmetric aldol reaction stands as a classic experiment illustrating the concept of enantiomerism. However, due to substrate reactivity limitations and experimental constraints, the stereochemical concepts of diastereoisomerism and racemization have not been adequately addressed. To bridge this gap between experimental and theoretical teaching and enhance students’ understanding of stereochemistry in Organic Chemistry, we have innovated and expanded the proline-catalyzed asymmetric aldol reaction. Firstly, by upgrading the conventional two-component reaction to a three-component reaction, we efficiently generate diastereomers through the conversion of arylaldehydes to highly reactive aldimines. Secondly, we introduce the stereoselective control of proline through the use of catalysts with opposite chiral configurations, while also incorporating the concept of racemization by mixing products with opposite configurations. Thirdly, we employ nuclear magnetic resonance (NMR) technology to elucidate the diastereoisomerism ratio of the products, facilitating a deeper understanding of diastereoisomerism concepts. Our results demonstrate that this experiment offers excellent repeatability, appropriate duration, and a balance of exploration and innovation. Implementation of this project not only enhances students’ scientific inquiry and innovative thinking but also cultivates their ability to conduct innovative experiments.

Key words:

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沈阳化工大学材料科学与工程学院沈阳 110142

脯氨酸催化的不对称羟醛缩合反应的改进与拓展

English

Advancements and Expansions in the Proline-Catalyzed Asymmetric Aldol Reaction

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

脯氨酸催化的不对称羟醛缩合反应的改进与拓展

English

Advancements and Expansions in the Proline-Catalyzed Asymmetric Aldol Reaction

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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通讯作者: 陈斌, bchen63@163.com

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