Acs Péter, Takács Attila, Szilágyi Antal, Wölfling János, Schneider Gyula, Kollár László
University of Pécs, Department of Inorganic Chemistry, Ifjúság u. 6, H-7624 Pécs, Hungary.
Steroids. 2008 Jul;73(6):669-75. doi: 10.1016/j.steroids.2008.02.002. Epub 2008 Feb 16.
17-Alkoxycarbonyl- and 17-carboxamido-13alpha-estra-1,3,5(10),16-tetraenes were synthesized from the 17-iodo-13alpha-estra-1,3,5(10),16-tetraene derivative in palladium-catalyzed alkoxycarbonylation and aminocarbonylation reactions, respectively. The synthesis of the 17-iodo-16-ene derivative, used as substrate, is based on the transformation of the 17-keto derivative (epiestrone methyl ether) to hydrazone, which was treated with iodine in the presence of a base (1,1,3,3-tetramethyl guanidine). 17-Carboxamides were obtained in good yields (up to 88%) not only with simple alkyl/aryl amines but also with amino acid methyl esters as N-nucleophiles. The use of alcohols as O-nucleophiles in alkoxycarbonylation resulted in the corresponding 17-esters; however, yields of synthetic interest were obtained only with methanol.
17-烷氧羰基-和17-羧酰胺基-13α-雌甾-1,3,5(10),16-四烯分别由17-碘-13α-雌甾-1,3,5(10),16-四烯衍生物通过钯催化的烷氧羰基化反应和氨羰基化反应合成。用作底物的17-碘-16-烯衍生物的合成基于17-酮衍生物（表雌酮甲醚）转化为腙，该腙在碱（1,1,3,3-四甲基胍）存在下用碘处理。17-羧酰胺不仅与简单的烷基/芳基胺，而且与氨基酸甲酯作为N-亲核试剂反应，都能以良好的产率（高达88%）得到。在烷氧羰基化反应中使用醇作为O-亲核试剂可得到相应的17-酯；然而，只有甲醇能得到具有合成价值的产率。
