Palladium-catalyzed regioselective C-H bond arylations at the C3 position of ortho-substituted fluorobenzenes

Anoir Hfaiedh (1, 2) , Hamed Ben Ammar (3) , Jean-François Soulé (1) , Henri Doucet (1)

1 ISCR - Institut des Sciences Chimiques de Rennes
2 UTM - Université de Tunis El Manar
3 FSM - Faculté des Sciences de Monastir

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.

Domains: Chemical Sciences; Organic chemistry; Chemical Sciences; Catalysis

Anoir Hfaiedh, Hamed Ben Ammar, Jean-François Soulé, Henri Doucet. Palladium-catalyzed regioselective C-H bond arylations at the C3 position of ortho-substituted fluorobenzenes. Organic & Biomolecular Chemistry, 2017, 15 (35), pp.7447-7455. ⟨10.1039/c7ob01689a⟩. ⟨hal-01614764⟩