Hfaiedh Anoir, Ben Ammar Hamed, Soulé Jean-François, Doucet Henri
UMR 6226 CNRS-Université de Rennes 1 "Organométalliques, Matériaux et Catalyse", Campus de Beaulieu, 35042 Rennes, France.
Org Biomol Chem. 2017 Sep 13;15(35):7447-7455. doi: 10.1039/c7ob01689a.
The influence of an ortho-substituent on fluorobenzene derivatives for palladium-catalyzed C-H bond arylation has been explored. In the presence of 2-bromo, 2-chloro and 2-methoxy substituents, the reaction proceeds nicely using a diphosphine-palladium catalyst and potassium acetate/dimethylacetamide (PivOK/DMA) as the catalytic system. In all cases, a regioselective arylation at the other ortho-position to the fluorine atom (C3) was observed. A variety of electron-withdrawing substituents on the aryl bromide coupling partner, such as formyl, nitro, nitrile, and also heteroaryl bromides, was tolerated. Moreover, tri(hetero)aryl derivatives containing a fluorobenzene as the central unit have been prepared from 2-bromofluorobenzene through palladium-catalyzed-successive C-H bond (hetero)arylations.
已对邻位取代基对氟苯衍生物用于钯催化的C-H键芳基化反应的影响进行了研究。在2-溴、2-氯和2-甲氧基取代基存在下，使用二膦钯催化剂和醋酸钾/二甲基乙酰胺（PivOK/DMA）作为催化体系时，反应顺利进行。在所有情况下，均观察到在氟原子的另一个邻位（C3）发生区域选择性芳基化反应。芳基溴偶联配偶体上的各种吸电子取代基，如甲酰基、硝基、腈基，以及杂芳基溴化物，均可耐受。此外，通过钯催化的连续C-H键（杂）芳基化反应，由2-溴氟苯制备了以氟苯为中心单元的三（杂）芳基衍生物。
