The palladium-catalyzed annulation of dienes and acetylenes has been further extended to include the enantioselective hetero- and carboannulation of 1,2- and 1,3-dienes, as well as the carboannulation of internal acetylenes using biaryls. These methodologies are remarkably general in scope and have proven to be extremely useful methods for the synthesis of a wide variety of hetero- and carbocycles. Thus, aryl and vinylic iodides with a nucleophilic substituent in the ortho or allylic position respectively, react with 1,2-dienes in the presence of a palladium catalyst and a chiral bisoxazoline ligand to afford five- and six-membered ring heterocycles and carbocycles in good yields and 46 to 88% enantiomeric excess. The generality of this process has been demonstrated by the use of nucleophilic substituents as varied as tosylamides, alcohols, carboxylic acids and stabilized carbanions. Likewise, many of these same aryl iodides react with 1,3-dienes under similar reaction conditions to afford five- and six-membered ring heterocycles in moderate enantiomeric excess. The annulation of acetylenes using palladium methodology has also been further extended to include the carboannulation of internal acetylenes using 2-iodobiaryls. This methodology provides an exceptionally efficient route to a variety of substituted polycyclic aromatic hydrocarbons, including synthetic analogues of the antiviral natural product hypericin.