Efficient access to 1,3,4-trisubstituted pyrroles via gold-catalysed cycloisomerization of 1,5-diynes.

A gold-catalysed cycloisomerization of 1,5-diynes is described, which offers a selective approach to access 1,3,4-trisubstituted pyrroles. In this reaction, the cationic gold catalyst activates the ynamide moiety, initiating the cycloisomerization to produce the pyrrole core, and H2O acts as an external nucleophile to trap the vinyl cationic species, thus leading to the formation of 1,3,4-trisubstituted pyrroles with high selectivity.

A Modular Approach to Dibenzo-fused ϵ-Lactams: Palladium-Catalyzed Bridging-C-H Activation.

Tricyclic ring systems possessing a dibenzo structure joined to a seven-membered heterocyclic ring frequently show important biological activities. However, a modular approach to these molecules based on efficient intermolecular reaction of readily available chemicals is lacking. Herein, an unprecedented palladium-catalyzed formal [4+3] annulation for modular construction of these tricyclic systems is described. This reaction features easily accessible reactants (o-haloarylaldehydes and N-tosylhydrazones), broad substrate scope, and excellent functional group compatibility. The synthetic potential is demonstrated by the easy scale-up reactions, late-stage modification of complex molecules, and collective synthesis of bioactive molecules and approved drugs.