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Direct difunctionalization of chemically distinct  ortho - and  peri -C–H bonds of fused hetero(arenes) is illustrated through an unusual one-pot domino {[4 + 2] &amp; [5 + 2]} double annulation with alkynes for the first time.

Double annulation of ortho- and peri-C–H bonds of fused (hetero)arenes to unusual oxepino-pyridines