Abstract
Two libraries of novel, bifunctional polycyclic cage structures have been synthesized for the first time in an ionic liquid, 1-butyl-3-methylimidazolium bromide ([bmim]Br), employing a sustainable microwave-assisted, one-pot, three-component [3+2] cycloaddition-annulation protocol in good to excellent yields. The ring systems thus generated contain as structural elements bridged, fused and spiro rings and were obtained with complete regio- and stereoselectivity through the creation of two C-C and two C-N bonds, which led to the generation of two azaheterocyclic rings and five adjacent stereogenic carbons, three of which are quaternary.