A mild procedure for the oxidative C−C cross‐coupling of tertiary anilines with phenols is described which provides the products generally in high yields and with excellent selectivity. The reaction is catalyzed by the hexadecafluorinated iron–phthalocyanine complex FePcF16 in the presence of substoichiometric amounts of methanesulfonic acid and ambient air as sole oxidant.

We describe the oxygenation of tertiary arylamines, and the amination of tertiary arylamines and phenols. The key step of these coupling reactions is an iron-catalyzed oxidative CÀ O or CÀ N bond formation which generally provides the corresponding products in high yields and with excellent regioselectivity. The transformations are accomplished using hexadecafluorophthalocyanineÀ iron(II) (FePcF 16 ) as catalyst in the presence of an acid or a base additive and require only ambient air as sole oxidant.

We describe the synthesis and photophysical properties of tetraarylnaphthidines. Our synthetic approach is based on an iron-catalyzed oxidative C–C coupling reaction as the key step using a hexadecafluorinated iron–phthalocyanine complex as a catalyst and air as the sole oxidant. The N,N,N’,N’-tetraarylnaphthidines proved to be highly fluorescent with quantum yields of up to 68%.