Pyrrolyl and indolyl derivatives of azaaromatics have been prepared by an aerobic photo-induced oxidative C–H/C–H coupling method in the presence of nanosized TiO2.

A novel, mild, and practical method of amination of simple nonfunctionalized arenes under metal free conditions has been developed. The approach allows coupling of electron-rich arenes with amino derivatives of electron-deficient heterocycles providing rapid access to scaffolds of bioactive compounds and is based on the application of the hypervalent iodine(III) reagent as an oxidant. Regioselective functionalization of C-H bonds of arenes by the formation of C-N bonds under organocatalytic conditions was demonstrated.

A versatile synthetic protocol was proposed for the direct C–C coupling of a ferrocene fragment with various azaheterocycles in the absence of metal catalysts on the basis of nucleophilic substitution of hydrogen. Monosubstituted and disubstituted heteroannular azinyl derivatives of ferrocene were prepared in good yields. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)