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Direct cross-dehydrogenative coupling of different inert CÀ H bonds is the most straightforward and environmentally benign method to construct CÀ C bonds. In this paper, we developed an iron-catalyzed intramolecular cross-dehydrogenative arylation (CDA) between benzylic C(sp 3 )H bond and aromatic C(sp 2 )H bond. From the readily available linear substrates, 1-arylnaphthalenes and 4-arylcoumarins can be quickly constructed with moderate to good yield (18 examples, up to 73 % yield) in one step. Both symmetrical and unsymmetrical substrates with different functional groups could tolerate this system well to form the anticipated products. A radical initiated dehydrogenative cyclization-dehydrogenation tandem process was proposed.

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