一种钯催化剂催化不稳定多氟芳基硼酸及2-杂芳基硼酸的Suzuki-Miyaura偶联反应  

A Palladium Catalyst Allows for the Suzuki-Miyaura Coupling Reactions of Unstable Polyfluorophenyl and 2-heteroaryl Boronic Acids

作　　者：赵顺伟[1] 化林[1] 张垚 孔宏俊 周铎[1] 刘婷婷 陈辉[1] ZHAO Shunwei;HUA Lin;ZHANG Yao;KONG Hongjun;ZHOU Duo;LIU Tingting;CHEN Hui(Institute of Chemistry Co.,Ltd.Henan Academy of Sciences,Zhengzhou 450002,China)

机构地区：[1]河南省科学院化学研究所有限公司,河南郑州450002

出　　处：《山东化工》2024年第23期7-11,18,共6页Shandong Chemical Industry

基　　金：国家自然科学基金(项目号22001060);河南省科学技术厅河南省科学院科技研发计划联合基金(项目号225200810059);河南省科学院科技攻关项目(项目号242203034);河南省科学院基本科研业务费项目(项目号230603011、240603044、240603051)。

摘　　要：Suzuki-Miyaura交叉偶联反应是应用最广泛的构建C-C键方法之一。多氟苯基和五元杂环是合成药物中间体等不可缺少的基团,但在反应过程中发现含有多氟苯基硼酸和五元杂环硼酸结构的化合物,在碱性条件下会快速脱硼,限制了该反应的应用。我们合成了一种含单齿双芳基膦配体的钯催化剂,该催化剂能够在常温、弱碱条件下生成催化活性物质,从而减缓了硼酸分解促进偶联反应进行。在这种催化剂的作用下,多氟苯基硼酸、2-呋喃硼酸、2-噻吩硼酸和2-吡咯硼酸及其类似物可以在室温下快速与芳基卤化物进行偶联反应且高收率得到产物。The Suzuki-Miyaura cross-coupling reaction is one of the most important and widely used methods for the construction of carbon-carbon bonds.Polyfluorophenyl and pentagonal heterocycles are essential functional groups in the synthesis of pharmaceutical intermediates.However,during the reaction process,it was found that these boronic acids,such as polyfluorophenyl boronic acid and pentagonal heterocyclic boronic acid,can quickly remove boron under alkaline conditions,limiting the application of this reaction.We developed a palladium catalyst containing a monodentate bisarylphosphine ligand that forms the catalytically active species under mild conditions where boronic acid decomposition is slow.With this catalyst,Suzuki-Miyaura reactions of aryl halides with polyfluorophenyl,2-furan,2-thiophene,and 2-pyrroleboronic acids and their analogues proceed could give the desired products in excellent yields at room temperature in short reaction times.

关 键 词：Suzuki-Miyaura偶联 不稳定硼酸 钯催化剂 

分 类 号：TQ032[化学工程] TQ426.8