Free Amine-Directed Ru(II)-Catalyzed Redox-Neutral [4 + 2] C-H Activation/Annulation of Benzylamines with Sulfoxonium Ylides.

An external oxidant free Ru(II)-catalyzed C-H functionalization/annulation of primary benzylamines with sulfoxonium ylides has been developed for the synthesis of isoquinolines. The reaction utilizes free amine as a directing group, which is generally considered to be a poor directing group. This work presents the first example of Ru-catalyzed C-H functionalization of benzylamines under redox-neutral conditions. The detection of the amine-directed ruthenacyclic intermediate using high-resolution mass spectrometry corroborated the involvement of free amine as a directing group.