A new and selective palladium-catalyzed amination of the pyrido[3',3':4,5]pyrrolo[1,2-c]pyrimidine nucleus, the heterocyclic core of the variolin alkaloids, is described. The method allows the introduction of amino and aryl- and alkyjamino substituents on the C9 position in advanced precursors of variolin B and deoxyvariolin. (c) 2007 Published by Elsevier Ltd.