Yang Bo-Wen, Xu Jun, Pan Jie, Chu Xue-Qiang, Chen Jian-Ping, Xu Hao, Miao Chengping, Rao Weidong, Shen Zhi-Liang
Technical Institute of Fluorochemistry (TIF), School of Chemistry and Molecular Engineering, Nanjing Tech University, Nanjing 211816, China.
College of Biological, Chemical Science and Engineering, Jiaxing University, 118 Jiahang Road, Jiaxing 314001, China.
J Org Chem. 2025 Apr 25;90(16):5480-5486. doi: 10.1021/acs.joc.5c00099. Epub 2025 Apr 11.
A palladium-catalyzed decarboxylative cross-coupling of zinc polyfluorobenzoates with aryl fluorosulfates, which proceeded efficiently via C-O bond cleavage to afford the corresponding polyfluorinated biaryls in moderate-to-good yields, was developed. The reactions exhibited both good substrate scope and broad functional group compatibility, and it could be scaled-up easily. The synthetic simplicity and practicability of the reaction was further demonstrated by one-pot manipulation by directly mixing polyfluorobenzoic acid and Zn(OH) in the coexistence of aryl fluorosulfate and a palladium catalyst in one flask. Further studies showed that aryl fluorosulfate is more robust than other aryl halides and pseudohalides as a arylating reagent, and zinc polyfluorobenzoate is a more effective decarboxylative polyfluoroarylating agent than their magnesium and potassium counterparts.
开发了一种钯催化的多氟苯甲酸锌与芳基氟硫酸盐的脱羧交叉偶联反应，该反应通过C-O键裂解有效地进行，以中等到良好的产率得到相应的多氟联芳基化合物。该反应具有良好的底物范围和广泛的官能团兼容性，并且易于放大。通过在一个烧瓶中直接将多氟苯甲酸和Zn(OH)在芳基氟硫酸盐和钯催化剂共存的情况下进行一锅操作，进一步证明了该反应的合成简便性和实用性。进一步的研究表明，芳基氟硫酸盐作为芳基化试剂比其他芳基卤化物和拟卤化物更稳定，多氟苯甲酸锌作为脱羧多氟芳基化试剂比其镁和钾类似物更有效。
