Process for producing 7.beta.-substituted-aza-5.alpha.androstan-3-ones

A process for the synthesis of 7.beta.-Substituted 4-aza-5.alpha.-androstan-3-ones, comprising the steps of (a) oxidizing a compound of the formula ##STR17## where Alk is selected from the group consisting of C1-4 alkyl, allyl and C3-6 cycloalkyl;

• and where A is selected from the group consisting of hydrogen, dimethyl-t-butyl silyloxy, hydroxy, acetylamino, amino, C1-10 alkyl, stigmasterol, phenyl substituted C1-10 alkyl, pyridyl substituted C1-10 alkyl, C1-10 carboalkoxy, C1-10 alkylcarboxamide, carboxy, and C1-10 alkylcarbonylamino urea;
• said compound oxidized in the presence of aluminum isopropoxide and cyclohexanone to form a compound of the formula ##STR18## (b) contacting the product of step (a) with a reducing system comprised of metallic lithium and liquid ammonia in an inert organic solvent therefor at a temperature in the range of about -45.degree. to -78.degree. for a sufficient time to stereo-selectively produce the 7.beta. compound of the formula:
• ##STR19## (c) contacting the product of step (b) with a double bond isomerization agent selected from the group consisting of 1,8-diazabicyclo[5.4.0]undec-7-ene, diisopropylethylamine and diazabicyclo[4.3.0]non-5-ene, in an inert organic solvent therefor, at a temperature of 40.degree. to 65.degree., under conditions in which the radical A is inert, for a sufficient time to form the isomerized compound of the formula:
• ##STR20## (d) contacting the product of step (c) with an oxidizing agent selected from the group consisting of potassium permanganate, sodium periodate, ruthenium tetraoxide and ozone;
• in an inert solvent therefor, at a temperature in the range of 23.degree. to 80.degree. under conditions in which radical A is inert, for a sufficient time to form the seco acid of the formula:
• ##STR21## (e) contacting the product of step (d) with an amine of the formula R--NH.sub.2, wherein R is H, C1-4 alkyl, benzyl or allyl, at a temperature of from 100.degree. to 200.degree. in an inert solvent therefor, under conditions in which A is inert, to form the 4-aza-steroid of the formula:
• ##STR22## (f) and contacting the product of step (e) with a platinum catalyst in an inert organic solvent, at room temperature, under conditions where A is inert, for a sufficient time to form the 7-Alk-4-aza steroid of the formula:
• ##STR23##