Abstract: The novel process of this invention involves the reduction of certain .DELTA.-5 steroidal alkenes to selectively produce either the 5.alpha. or 5.beta. reduction products. Particularly, this invention involves reduction of .DELTA.-5 steroidal alkenes using a rhodium based catalyst in the presence of hydrogen to selectively yield 5.alpha. steroids or alternatively reduction of .DELTA.-5 steroidal alkenes in an ionizing medium with a trialkylsilane to selectively yield 5.beta. steroids.