Regio- and Chemoselective Formal (4+1) Carbocyclization of Chalcones with Internal Alkynes via Rhodium(III) Catalysis.

A rhodium(III)-catalyzed oxidative cyclization of chalcones with internal alkynes is reported, generating biologically important 3,3-disubstituted 1-indanones along with reusable aromatic aldehydes. This transformation features unique (4+1) reaction mode, excellent regioselectivity in alkyne insertion, broad substrate scope, allows for the construction of quaternary carbon centers, and is scalable. Steric hindrance from substrate and ligand probably controls the chemoselectivity of this carbocyclization. Importantly, this discovery enables a practical two-step protocol switching the overall reaction of acetophenones with internal alkynes from a (3+2) to a (4+1) annulation.

Rhodium(III)-Catalyzed Intramolecular Annulation and Aromatization for the Synthesis of Pyrrolo[1,2-a]quinolines.

A rhodium(III)-catalyzed protocol for the synthesis of pyrrolo[1,2-a]quinolines through intramolecular annulation of o-alkynyl amino aromatic ketones and subsequent aromatization is reported. This transformation builds the pyrrole and quinoline moieties of the pyrrolo[1,2-a]quinoline in one pot and achieves a flexible introduction of different substituent groups at 4- and 5-positions on products that were difficult to prepare by other means. The reaction proceeds smoothly on a gram scale, and the products are amenable to downstream synthetic manipulations.