Iron‐Catalyzed Oxidative C−O and C−N Coupling Reactions Using 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 C−O or C−N bond formation which generally provides the corresponding products in high yields and with excellent regioselectivity. The transformations are accomplished using hexadecafluorophthalocyanine−iron(II) (FePcF16) as catalyst in the presence of an acid or a base additive and require only ambient air as sole oxidant. [ABSTRACT FROM AUTHOR]