Push-pull dipoles generated from the Rh (II)-catalyzed reaction of diazo imides containing tethered heteroaromatic rings undergo successful [3+ 2]-cycloaddition across the 2, 3-π- bond to provide novel pentacyclic compounds in good to excellent yields in a stereocontrolled fashion. The facility of the cycloaddition is critically dependent on conformational factors in the transition state.
