Efficient construction of novel carbocyclic frameworks via intramolecular aromatic addition of diazoketones followed by Diels-Alder cycloaddition

Rhodium catalysed intramolecular aromatic additions of diazoketones followed by Diels-Alder cycloadditions with carbon-based dienophiles leads in a highly stereoselective manner to polycyclic frameworks containing eight stereogenic centres completely controlled by the single stereocentre present in the diazoketone precursor. These cycloadditions provide interesting mechanistic insight into a dynamic equilibrium in methoxy-substituted azulenones.