Hydroformylation – amidocarbonylation of androstene and pregnene derivatives

Androstene and pregnene derivatives were functionalized by amides with rhodium or binary rhodium–cobalt catalysts. Whereas the Rh–PPh₃ catalyzed reaction results in the unsaturated amido‐methylidene derivatives, the rapid hydrogenation of these compounds takes place in the presence of a basic PR₃ ligand. Using a binary rhodium–cobalt system, amidocarbonylation of the steroids occurs with high chemo‐ and regio‐selectivity. Our experiments did not support literature reports claiming the essential role of a bimetallic cluster as the active catalyst. Copyright © 2002 John Wiley & Sons, Ltd.