Novel synthetic routes to thienocarbazoles via palladium or copper catalyzed amination or amidation of arylhalides and intramolecular cyclization

Palladium or copper catalyzed aminations or amidations were performed to obtain diarylamines and diarylacetamides precursors of thienocarbazoles. The fact that an ortho-bromodiarylamine did not cyclize to the corresponding thienocarbazole under conditions known for carbazoles from ortho-halodiphenylamines, conducted us to a highly efficient method of palladium-catalyzed intramolecular cyclization with N-deprotection of ortho-halodiarylacetamides to thienocarbazoles. Other method of intramolecular cyclization of diarylamines based on the reoxidation of the Pd(0) formed by Cu(OAc)(2), avoiding the use of stoichiometric amounts of Pd(OAc)(2), gave thienocarbazoles in a moderate yield, including a ring A methoxylated compound. An attempt to combine palladium and copper catalyses in a 'one pot' reaction of amination and intramolecular cyclization gave as major product a N-benzo[b]thiophene substituted carbazole and the required thienocarbazole in low yield. (C) 2002 Elsevier Science Ltd. All rights reserved.