Palladium(II)/Lewis Acid Cocatalyzed Oxidative Annulation of 2-Alkenylanilines and Propargylic Esters: An Access to Benzo[b]azepines.

An attractive approach to valuable yet synthetically challenging benzo[b]azepines was established via palladium(II)/Lewis acid cocatalyzed oxidative [5 + 2] annulation of readily available 2-alkenylanilines and propargylic esters. The protocol features mild reaction conditions and good functional group tolerance, constituting an array of benzo[b]azepines in yields of 30-75%.

Enantioselective Synthesis of Functionalized Tetrahydropyridines through Iridium-Catalyzed Formal [5+1] Annulation.

An efficient iridium-catalyzed asymmetric formal [5+1] annulation by in situ generation of enamines as N-nucleophiles for the synthesis of tetrahydropyridine derivatives is disclosed. The methodology offers direct access to a wide variety of chiral tetrahydropyridine derivatives in moderate to good yields and excellent enantioselectivity.

N-Heterocyclic Carbene-Catalyzed Atroposelective Synthesis of Pyrrolo[3,4-b]pyridines with Configurationally Stable C-N Axial Chirality.

The first atroposelective synthesis of pyrrolo[3,4-b]pyridines catalyzed by N-heterocyclic carbene has been achieved. A wide range of chiral atropisomers of pyrrolo[3,4-b]pyridines were obtained in high yields with excellent enantioselectivities (96-99% enantiomeric excess). The experimental results and density functional theory calculations showed that the C-N axial chirality of the product had high thermal stability.