A palladium-catalyzed multicomponent route topolycyclic pyrroles is described. Pd(PtBu3)2was found tocatalyze the coupling of (hetero)aryl iodides, two equivalentsof carbon monoxide and alkyne-tethered imines into 1,3-dipoles (Münchnones), which undergo spontaneous, intra-molecular 1,3-dipolar cycloaddition to form polycyclicpyrroles. The systematic variation of the alkyne, tethered-imine, or aryl iodide can allow the buildup of a range of pyrrolederivatives, where any of the substituents can be independentlyvaried. In addition, the same palladium catalyst can beemployed in an initial Sonogashira-type coupling with aryl iodides, which upon the addition of CO can allow the noveltandem catalytic,five component synthesis of diversely substituted products.

Keywords