近日，中国海洋大学王洪玉团队实现了NHC催化自由基交叉缩合合成多种β-酮酯。2025年8月7日出版的《中国化学》杂志发表了这项成果。

交叉克莱森缩合是合成β-酮酯的一种有价值的方法，但传统上受限于需要强碱或预成型的硅基酮缩醛（SKAs）或底物范围狭窄。

为了解决这些问题，研究组在酰基咪唑和α-溴酯之间建立了一种温和的N-杂环碳（NHC）催化的自由基交叉克莱森缩合反应。该方案采用Mn介导的单电子还原生成持久的酮基和α-羰基自由基，使两种亲电试剂在氧化还原-中性条件下有效交叉偶联。该反应具有广泛的官能团耐受性，可以直接从羧酸中进行一锅反应，为β-酮酯的合成提供了一个实用的平台。

附：英文原文

Title: NHC-Catalyzed Radical Cross-Claisen Condensation for Diverse β-Keto Ester Synthesis

Author: Xiangyu Zhuang, Hao Li, Hongyu Wang

Issue&Volume: 2025-08-07

Abstract: The cross-Claisen condensation is a valuable method for synthesizing β-keto esters but is traditionally limited by the need for strong bases or preformed silyl ketene acetals (SKAs) or a narrow substrate scope. To address these challenges, we developed a mild, N-heterocyclic carbene (NHC)-catalyzed radical cross-Claisen condensation between acyl imidazoles and α-bromo esters. This protocol employs Mn-mediated single-electron reduction to generate persistent ketyl and α-carbonyl radicals, enabling efficient cross-coupling of two electrophiles under redox-neutral conditions. The reaction proceeds with broad functional-group tolerance and can be conducted in a one-pot manner directly from carboxylic acids, offering a practical platform for β-keto ester synthesis.

DOI: 10.1002/cjoc.70214

Source: https://onlinelibrary.wiley.com/doi/10.1002/cjoc.70214