Free Amine-Directed Redox Neutral Ruthenium(II) Catalysis toward Regioselective Synthesis of Heterobiaryls.

A regioselective coupling of ortho-heteroaryl anilines and 7-oxabenzonorbornadienes has been developed by leveraging free amine-directed redox-neutral Ru(II) catalysis. This protocol facilitates formal C-2 arylation of the indole moiety under mild conditions to offer valuable heterobiaryls in high yields. The reaction displays a broad substrate generality and scalability and retains efficacy in the presence of diverse pharmacophore scaffolds. Moreover, products bearing a free amine group were successfully employed in Mg(NTf2)2-catalyzed double Michael addition cascade, which led to the synthesis of intricate indole- and pyrrole-fused azaheterocycles.

Regioselective Annulation of Allenylphosphine Oxides with Aromatic Amides under Ruthenium(II) Catalysis.

Engaging allenes in transition-metal-catalyzed C-H bond activation strategy is immensely promising to access high-value scaffolds. However, such a reaction manifold remains largely elusive using cheap and sustainable ruthenium catalysis. We disclose an unprecedented ruthenium-catalyzed (4 + 2) annulation between aromatic amides and allenylphosphine oxides, furnishing NH-free isoquinolinones in high yields. This operationally simple methodology leverages weak coordination assistance, displays high selectivity, and is amenable to the late-stage functionalization of several biologically relevant motifs.