A mild, practical protocol for the decarboxylative alkylation of heteroarenes has been accomplished via iron photocatalysis. A diverse range of carboxylic acids readily undergo oxidative decarboxylation and then couple with a broad array of heteroarenes in this transformation. The photoexcited state lifetimes of iron complexes are typically much shorter than those of iridium and ruthenium complexes. Here we describe our effort on iron photocatalysis by utilizing the intramolecular charge transfer pathway of iron−carboxylate complexes.

A mild and efficient protocol for the intramolecular aromatic C–H oxygenation of 2-biphenylcarboxylic acids has been achieved via iron photocatalysis. The 2-biphenylcarboxylic acids with a diverse array of substituents at both phenyl rings could furnish the oxygenation products in good to excellent yields. We speculate that the aryl carboxylate–iron­(III) complexes should generate the aroyloxy radicals and iron­(II) upon visible light irradiation.

An efficienta nd operationally simple Ni-catalyzed aminationp rotocol has been developed.T hism ethodologyf eatures as imple Ni II salt, an organic base and catalytic amountso fb oth ap yridinium additive and Zn metal. Ad iversen umber of (hetero)aryl halides were coupled successfully with primary ands econdary alkyl amines, and anilines in good to excellent yields. Similarly, benzophenone imine gave the corresponding N-arylation product in an excellenty ield.