A new method for regiocontrolled pyridine synthesis has been developed involving sequential Rh(I)-catalyzed chelation-assisted hydroacylation of alkynes with aldehydes followed by Rh(III)-promoted N-annulation of the resulting α,β-enones with another alkyne and NH(3).

Rh(iii)/Cu(OAc)2 catalyzed, one-pot reactions of aryl ketones, acrylate esters and ammonium acetate or α-substituted benzylamines under microwave irradiation conditions produce 1H-isoindoles bearing a quarternary carbon center.

New Rh(III)-catalyzed, one-pot N-annulation reactions of aryl and α,β-unsaturated ketones with alkynes in the presence of ammonium acetate have been developed. Under microwave irradiation conditions, the processes lead to rapid formation of the respective isoquinoline and pyridine derivatives with efficiencies that are strongly dependent on the steric nature of the aryl ring and enone substituents. By employing this protocol, a variety of isoquinoline and pyridine derivatives were prepared in high yields. In addition, a new one-pot approach to the synthesis of pyridines, involving four-component reactions of ketones, formaldehyde, NH(4)OAc, and alkynes, has been uncovered. This process takes place through a route involving initial aldol condensation of the ketone with formaldehyde to generate a branched α,β-unsaturated ketone that then undergoes Rh(III)-catalyzed N-annulation with NH(4)OAc and the alkyne