3-Aroyl-1 H-pyrrolo[2,1- c][1,4]benzoxazine-1,2,4-triones reacted with alkyl vinyl ethers according to the [4 + 2]-cycloaddition pattern with formation of substituted (1 S*,16 R*)- and (1 R*,16 R*)-16-alkoxy-14-aryl-3,15-dioxa-10-azatetracyclo[8.7.0.0...

Polycyclic structures fused at a central carbon are of great interest due to their appealing conformational features and their structural implications in biological systems. Although progress in the development of synthetic methodologies towards such structures has been impressive, the stereoselective construction of such quaternary stereocentres remains a significant challenge in the total synthesis of natural products. This review summarises a series of studies on the reactions of 1H-pyrrole-2,3- diones with nucleophiles and highlights the progress in the formation of new polyheterocyclic compounds with concomitant formation of the quaternary spiro centre.