近日，香港中文大学Hairong Lyu团队研究了电化学去氟马特森型同质化。2026年1月7日出版的《自然》杂志发表了这项研究成果。

马特森同系化反应最早于1980年开发，通过插入碳-硼（C−B）键来延长碳链。这一多功能反应传统上需要三个步骤：碳负离子形成、对有机硼的亲核加成以及热或路易斯酸促进的硼酸酯重排。这些过程通常需要严格的条件，包括低温条件以及处理对空气和水分敏感的试剂。

研究组报道了一种马特森型同系化反应，该反应将这三个转化过程整合到一个一锅电化学过程中。这种概念验证方法将电还原脱氟与硼酸酯重排相结合，无需使用有机锂试剂、低温条件或专业设备。首次将可用的三氟甲基芳烃用作卡宾前体，从而扩大了马特森反应的应用范围。通过全面的机理研究，包括关键反应中间体的鉴定、密度泛函理论（DFT）计算和电化学分析，证实了硼酸酯形成和重排参与了这种“电子马特森”同系化反应。

附：英文原文

Title: Electrochemical defluorinative Matteson-type homologation

Author: Cheung, Tsoh Lam, Li, Yujun, Zhang, Peiqi, Yang, Zhiyi, Quan, Yangjian, Lyu, Hairong

Issue&Volume: 2026-01-07

Abstract: The Matteson homologation, first developed in 1980, elongates carbon chains by insertion into a CB bond.1 This versatile reaction traditionally requires three steps: carbanion formation, nucleophilic addition to organoboron, and a thermo- or Lewis acid-promoted boronate rearrangement. These processes often demand exacting conditions, including cryogenic temperatures and handling of air- and moisture-sensitive reagents.2,3 Here, we report a Matteson-type homologation which integrates these three transformations into a one-pot electrochemical process. This proof-of-concept approach combines electroreductive defluorination with boronate rearrangement, eliminating the need for organolithium reagents, cryogenic conditions, or specialist setups. The available trifluoromethylarenes are employed as carbenoid precursors for the first time, expanding the scope of Matteson reaction. Comprehensive mechanistic studies, including identification of key reaction intermediates, DFT calculations, and electrochemical analysis, confirm the involvement of boronate formation and rearrangement in this “e-Matteson” homologation.

DOI: 10.1038/s41586-025-10002-4

Source: https://www.nature.com/articles/s41586-025-10002-4