Patent ID: 7872135

Claim:
A process for preparing 17β-substituted 4-azaandrost-1-en-3-one compounds of the general formula (I): where R is hydroxyl, optionally substituted, linear or branched (C 1 -C 12 )alkyl or (C 1 -C 12 )alkenyl; phenyl or benzyl; an —OR 1 radical, or an —NHR 1 radical, or an —NR 1 R 2 radical; R 1 is hydrogen, optionally substituted, linear or branched (C 1 -C 12 )alkyl or (C 1 -C 12 )alkenyl, or optionally substituted phenyl; R 2 is hydrogen, methyl, ethyl or propyl; or —NR 1 R 2 is a 5- or 6-membered heterocyclic ring, and when R=hydroxyl also a pharmaceutically approved salt thereof, characterized in that (A) protecting groups are introduced into the 3-keto-4-aza moiety (lactam moiety) of a compound of the general formula (II): so that a compound of the general formula (III) is formed: where R 3 is trialkylsilyl or, together with R 4 , the —C(O)—C(O)— or —C(O)—Y—C(O)— radical; R 4 is alkyloxycarbonyl or phenyloxycarbonyl, Boc (=tert-butyloxycarbonyl); or tri-alkylsilyl, or, together with R 3 , the —C(O)—C(O)— or —C(O)—Y—C(O)— radical; Y is —[C(R 5 )(R 6 )] n — or —CH(R 5 )═CH(R 6 )—, or ortho-phenylene; R 5 and R 6 are each independently hydrogen, linear or branched (C 1-8 )alkyl or alkenyl, optionally substituted phenyl or benzyl; and n is an integer of 1 to 4; and where, in the case that R is hydroxyl, it has optionally reacted with a protecting group; (B) the compound obtained [in step (A)] is reacted in the presence (i) of a dehydrogenation catalyst selected from the group comprising catalytically active Pd(0) compounds, the tris(dibenzylidineacetone)dipalladium-chloroform complex and Pd(II) compounds. said Pd(II) compounds being selected from the group consisting of PdCl 2 , Pd(dppe) 2 , [dppe =bis(1.2-biphenyl phosphino)ethane], Pd(dppe)Cl 2 , Pd(OAc) 2 , and Pd(dppe)(OAc) 2 and from π-allyl-Pd complexes, including π-allyl-Pd chloride dimer, and mixtures thereof and in the presence of (ii) optionally substituted benzoquinone, allyl methyl carbonate, allyl ethyl carbonate and/or allyl propyl carbonate, and the Δ l double bond is introduced in the 1-/2-position, and (C) the protecting groups R 3 and R 4 are removed and when R=hydroxyl the resulting compound is optionally converted to a salt.