•Domino C–H/N–H bond functionalizations.•Ruthenium complexes.•Oxidative annulation reaction.•Efficient access to isoquinolines.•Open-flask condition.Ruthenium(II) complexes catalyzed tandem C–H/N–H bonds functionalizations of 2-phenyl imidazole and its derivatives with alkynes were realized. This transformations allowed for rapid synthesis of isoquinoline derivatives under open-flask condition.Ruthenium catalyzed oxidative annulation with alkyne via cascade C–H/N–H bond functionalization, which efficiently provided structure-complex isoquinolines.

We report herein the first example of intramolecular cyanation of a styrene by a rhodium(I)-catalyzed N–CN cleavage reaction. Substituents on the arenes or the styrene alpha-position are tolerated. Our results demonstrate that alkene cyanation can indeed be atom economical.

We report herein the first example of intramolecular cyanation of a styrene by a rhodium(I)-catalyzed N–CN cleavage reaction. Substituents on the arenes or the styrene alpha-position are tolerated. Our results demonstrate that alkene cyanation can indeed be atom economical.