Abstract
The reactivity of positions C9 and C10 of 9‐ or 10‐bromophenanthrenes in palladium‐catalyzed direct heteroarylations was investigated. A wide variety of heteroarenes such as thiazoles, (benzo)thiophenes, (benzo)furans, pyrroles, selenophenes or imidazopyridazines was successfully introduced at phenanthrene C9‐position via palladium‐catalyzed direct arylations, using 0.5–0.1 mol‐% of phosphine‐free Pd(OAc)2 catalyst. Then, C10‐bromination of the 9‐heteroarylated phenanthrenes, followed by a second palladium‐catalyzed direct heteroarylation gives access to symmetrical and non‐symmetrical 9,10‐di(heteroaryl)phenanthrenes.
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