The synthesis of 13alpha-androsta-5,16-diene derivatives with carboxylic acid, ester and carboxamido functionalities at position-17 via palladium-catalyzed carbonylation.

17-Alkoxycarbonyl- and 17-carboxamido-3beta-hydroxy-13alpha-androsta-5,16-diene derivatives were synthetized in high yields in the palladium-catalyzed carbonylation reactions of the corresponding 3beta-hydroxy-17-iodo-13alpha-androsta-5,16-diene. This substrate with a 17-iodo-16-ene functionality was obtained from the 17-keto derivative via its 17-hydrazone, which was treated with iodine in the presence of a base (1,1,3,3-tetramethylguanidine). 17-Carboxamides were obtained by chemoselective aminocarbonylation through the use of amines, including amino acid esters, as N-nucleophiles. The 17-methoxycarbonyl-16-ene derivative was synthetized by using methanol as O-nucleophile. The parent compound of this series, the 17-carboxylic acid derivative, was formed in the presence of water via hydroxycarbonylation.