A diverse array of isoquinolines and phenanthridines have been accessed by developing a two-step, one-pot method constituting regioselective palladium-catalyzed Kuwajima-Urabe α-arylation of silylenol ethers and acid-mediated deprotection, annulation, and aromatization. Structural diversity in the silylenol ethers leads to three different classes of isoquinolines and phenanthridines from which related natural products can be derived. The synthetic utility of this method by the quick assembly of the natural product trispheridine is also demonstrated.

A new unified strategy has been developed for the synthesis of substituted 2-alkenylindoles and carbazoles. The strategy uses palladium-catalyzed α-arylation of TES-enol ethers of enones as the key step. The method is highly regioselective, provides good yields, and is expected to have wide application.

A simple procedure for the intermolecular enantioselective palladium-catalyzed decarboxylative allylation of β-ketoacids is described. This method, inspired by a stoichiometric control experiment performed by Saegusa and co-workers some 40+ years ago, makes use of allyl carbonates as the coupling substrates and enables direct access to α-allylated ketones bearing newly formed quaternary stereocenters. Experiments suggest that the transformation proceeds via an inner-sphere mechanism and not the traditional outer-sphere process proposed. The reaction should be highly useful and its application is demonstrated by a short enantioselective synthesis of (+)-adalinine.

Asymmetric allylic alkylation (AAA) is a powerful method for the formation of highly useful, non-racemic allylic compounds. Here we present a complementary enantioselective process that generates allylic lactones via p-acid catalysis. More specifically, a catalytic enantioselective dehydrative lactonization of allylic alcohols using a novel Pd II -catalyst containing the imidazole-based P,N-ligand (S)-StackPhos is reported. The high-yielding reactions are operationally simple to perform with enantioselectivities up to 99 % ee. This strategy facilitates the replacement of a poor leaving group with what would ostensibly be a better leaving group in the product avoiding complications arising from racemization by equilibration.

Asymmetric allylic alkylation (AAA) is a powerful method for the formation of highly useful, non‐racemic allylic compounds. Here we present a complementary enantioselective process that generates allylic lactones via π‐acid catalysis. More specifically, a catalytic enantioselective dehydrative lactonization of allylic alcohols using a novel PdII‐catalyst containing the imidazole‐based P,N‐ligand (S)‐StackPhos is reported. The high‐yielding reactions are operationally simple to perform with enantioselectivities up to 99 % ee. This strategy facilitates the replacement of a poor leaving group with what would ostensibly be a better leaving group in the product avoiding complications arising from racemization by equilibration.