Androstene and pregnene derivatives were functionalized by amides with rhodium or binary rhodium±cobalt catalysts. Whereas the Rh±PPh 3 catalyzed reaction results in the unsaturated amidomethylidene derivatives, the rapid hydrogenation of these compounds takes place in the presence of a basic PR 3 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.

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