Palladium and Nickel Catalyzed Hydroxycarbonylation of a Steroidal Bromodiene in the Synthesis of Episteride, a Potent 5α-Reductase Inhibitor

Androst-4-en-3-one-17 beta-carboxylic acid 1 was converted to 3-bromo-N-(1,1-dimethylethyl) androsta-3,5-diene-17-beta-carboxamide 2 by reaction with DMF/oxalyl bromide and quenching into t-butylamine. 2 was converted to 3 (R=H) by nickel cyanide catalyzed hydroxycarbonylation or palladium (0) catalyzed hydroxycarbonylation.