Abstract
This chapter summarizes the up‐to‐date reports on the transition metal‐catalysed direct arylation of unactivated arenes with aryl halides. Compared to the traditional coupling reactions, the direct arylation of arenes especially unactivated arenes via C–H bond activation, in which the obligation of prefunctionalization could be avoided, has attracted increasing interest. Noble transition metals were first employed to catalyse the direct arylation of unactivated arenes while cheap transition metal catalyzed direct arylation were later developed. Relevant mechanistic studies showed that radical species might be involved in many transformations. However, although great improvements have been made in this type of reaction, challenges such as regioselectivity, substrate scope and mild conditions still remain, and further developments on these problems are expected.
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