人工酶催化环己酮的羟醛缩合反应研究
本文介绍了一种基于烯胺催化模式的人工酶催化环己酮的羟醛缩合反应。羟醛缩合反应涉及烯醇负离子对醛/酮的亲核加成,是有机化学中形成碳-碳键的重要反应之一。本研究通过蛋白质共价连接的策略,设计了一种含有仲胺催化基团的人工酶,该人工酶通过烯胺模式活化羰基,催化中心与环己酮形成亲核性烯胺中间体,催化环己酮与吲哚醌发生羟醛缩合反应。根据目标反应的性质进行了反应条件优化,并确认此人工酶在优化条件下成功催化该反应的发生,反应结果通过高效液相进行了验证。尽管当前反应的立体选择性和收率尚未达到理想水平,但这一研究为人工酶催化环酮分子的羟醛缩合反应提供了可能性,也为人工酶的设计和非天然功能开发奠定了一定的理论基础。
he aldol reaction of cyclohexanone catalyzed by an artificial enzyme via the enamine mechanism was investigated. The aldol reaction involves the nucleophilic addition of enolate anions to aldehydes or ketones, representing one of the key reactions in organic chemistry for forming carbon-carbon bonds. In this study, an artificial enzyme incorporating secondary amine catalytic groups was designed via a protein covalent linking strategy. This artificial enzyme activated the carbonyl group through the enamine mechanism, catalyzed the formation of nucleophilic enamine intermediates with cyclohexanone, and facilitated the aldol reaction between cyclohexanone and indole quinone. Reaction conditions were systematically optimized according to the characteristics of the target reaction, and it was confirmed that the artificial enzyme successfully catalyzed the reaction under optimized conditions. The reaction results were validated using high-performance liquid chromatography (HPLC). Although the stereoselectivity and yield of the current reaction have yet to reach ideal levels, this study demonstrates the potential of artificial enzymes to catalyze aldol condensation reactions involving cycloketone molecules. Furthermore, it provides a theoretical basis for the design of artificial enzymes and the development of unnatural catalytic functions.?????
凤良玉、周志
江南大学生命科学与健康工程学院,无锡,214122江南大学生命科学与健康工程学院,无锡,214122
生物化学生物工程学
人工酶、生物催化、蛋白共价连接、羟醛缩合反应、生物合成
rtificial enzymes BiocatalysisCovalent conjugationAldol reaction Biosynthesis
凤良玉,周志.人工酶催化环己酮的羟醛缩合反应研究[EB/OL].(2025-03-31)[2025-06-03].http://www.paper.edu.cn/releasepaper/content/202503-312.点此复制
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