Acs Péter, Takács Attila, Szilágyi Antal, Wölfling János, Schneider Gyula, Kollár László
Department of Inorganic Chemistry, University of Pécs, Ifjúság u. 6, H-7624 Pécs, Hungary.
Steroids. 2009 Apr-May;74(4-5):419-23. doi: 10.1016/j.steroids.2008.12.009. Epub 2008 Dec 30.
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.
17-烷氧羰基和17-羧酰胺基-3β-羟基-13α-雄甾-5,16-二烯衍生物是在相应的3β-羟基-17-碘-13α-雄甾-5,16-二烯的钯催化羰基化反应中以高产率合成的。这种具有17-碘-16-烯官能团的底物是由17-酮衍生物通过其17-腙得到的，该腙在碱（1,1,3,3-四甲基胍）存在下用碘处理。通过使用胺（包括氨基酸酯）作为N-亲核试剂进行化学选择性氨基羰基化反应得到17-羧酰胺。通过使用甲醇作为O-亲核试剂合成了17-甲氧基羰基-16-烯衍生物。该系列的母体化合物，即17-羧酸衍生物，是在水存在下通过羟基羰基化反应形成的。
