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.
Acs
Péter
P
Department of Inorganic Chemistry, University of Pécs, Ifjúság u. 6, H-7624 Pécs, Hungary.
Takács
Attila
A
Szilágyi
Antal
A
Wölfling
János
J
Schneider
Gyula
G
Kollár
László
L
D000577:Amides / Q000737:chemistry*; D000730:Androstadienes / Q000138:chemical synthesis* / Q000737:chemistry*; D002264:Carboxylic Acids / Q000737:chemistry*; D002384:Catalysis; D004952:Esters / Q000737:chemistry*; D010165:Palladium / Q000737:chemistry*
D000577:Amides; D000730:Androstadienes; D002264:Carboxylic Acids; D004952:Esters; D010165:Palladium