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

Organic & Biomolecular Chemistry Pub Date: 2017-08-14 DOI: 10.1039/C7OB01689A

Abstract

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.

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