Facile synthesis of 11-carboxamido-androst-4,9(11)-dienes via palladium-catalyzed aminocarbonylation

11-Carboxamido-androst-4,9(11)-dienes were synthesized from the corresponding 11-iodo-androst-4,9(11)-diene derivative in palladium-catalyzed aminocarbonylation reaction under mild reaction conditions. The synthesis of the iodo-alkene substrate is based on the transformation of the 11-keto derivative to hydrazone, which was treated with iodine in the presence of a base (1,1,3,3-tetramethyl guanidine). The 11-carboxamides were synthesized in moderate to high isolated yields by using simple alkyl/arylamines or amino acid methylesters as N-nucleophiles. The highly active palladium catalysts enable the homogeneous catalytic functionalization at one of the most hindered position (C-11) of the steroidal skeleton.