Zhang Chun, Cui Yangbo, Zhou Xiaoyu, Pan Yichen, Zhang Junqi, Hu Dandan, Guo Hai-Ming, Hao Er-Jun, Ren Hongjun
School of Pharmaceutical and Chemical Engineering and Institute for Advanced Studies, Taizhou University, Taizhou 318000, China.
School of Chemistry and Chemical Engineering, Henan Normal University, Xinxiang 453007, China.
Org Lett. 2025 Mar 7;27(9):2256-2261. doi: 10.1021/acs.orglett.5c00408. Epub 2025 Feb 26.
We report a Pd-catalyzed decarboxylative Negishi coupling reaction for efficient biaryl synthesis from various zinc aryl carboxylates, including polyfluorobenzoates and heteroaryl carboxylates, using DMF as the solvent. This mild reaction exhibits a broad substrate scope and enables late-stage functionalization of bioactive molecules. Mechanistic studies show that DMF-assisted zinc catalyzes decarboxylation of polyfluorinated aryl carboxylates to generate arylzinc reagents in situ, which then undergo Negishi coupling catalyzed by palladium with arylthianthrenium salts to form biaryl compounds. Notably, this protocol represents a rare example of zinc-mediated decarboxylation and demonstrates a novel strategy for preparing arylzinc reagents from easily accessible (hetero)aryl carboxylic acids.
我们报道了一种钯催化的脱羧Negishi偶联反应，该反应以N，N-二甲基甲酰胺（DMF）为溶剂，能使各种芳基羧酸盐锌，包括多氟苯甲酸盐和杂芳基羧酸盐高效合成联芳基化合物。这种温和的反应具有广泛的底物范围，并能够实现生物活性分子的后期官能团化。机理研究表明，DMF辅助的锌催化多氟芳基羧酸盐的脱羧反应，原位生成芳基锌试剂，然后该试剂与芳基硫杂蒽鎓盐在钯催化下发生Negishi偶联反应，形成联芳基化合物。值得注意的是，该方法是锌介导脱羧的罕见例子，并展示了一种从易于获得的（杂）芳基羧酸制备芳基锌试剂的新策略。
