Efficient syntheses of 17-β-amino steroids

17β-Amino steroids such as 17β-amino-1,3,5(10)-estratrien-3-ol (1), 17β-amino-5α-androstan-3β-ol (2) and, 17β-amino-3β-hydroxyandrost-5-ene (3) have been widely used as a key intermediates in the synthesis of a variety of biologically active steroid derivatives though concise, high yielding syntheses of these compounds has yet to be reported. 17β-Amino-1,3,5(10)-estratrien-3-ol (1) and 17β-amino-5α-androstan-3β-ol (2) were prepared in high yield by reductive amination of estrone and epiandrosterone using benzylamine and sodium triacetoxyborohydride followed by catalytic hydrogenolysis of the resulting 17β-benzylamino derivatives. Attempts to prepare 17β-amino-3β-hydroxyandrost-5-ene (3) from dehydroepiandosterone using a similar approach resulted in partial reduction of the double bond. 17β-Amino-3β-hydroxyandrost-5-ene (3) was ultimately obtained in high yield by reductive amination of dehydroepiandosterone using allylamine and sodium triacetoxyborohydride followed by removal of the allyl group from the resulting 17β-allylamino derivative with dimethylbarbituric acid and Pd(PPh(3))(4) as catalyst.