title: Reaction of (13S)-13-iodo-6beta-methoxy-3alpha,5-cyclo-13,14-seco-5alpha-androstane-14,17-dione with hydroxylamine and its application to the synthesis of new 13,14-seco steroids.
abstract: The synthesis of 13,14-seco steroids starting from easily available (13S)-13-iodo-6beta-methoxy-3alpha,5-cyclo-13,14-seco-5alpha-androsta-14,17-dione is described. The C-17 ketone was converted regioselectively into its oxime with simultaneous stereoselective deiodination at C-13. The remaining C-14 carbonyl group was then reduced stereoselectively with Ca(BH4)2. The configurations at the relevant stereocenters of the thus obtained hydroxy oxime were determined by X-ray analysis. Successful regeneration of the C-17 carbonyl group was achieved by treatment of the corresponding oxime acetate with TiCl3.
authors.affiliation: Institute of Bioorganic Chemistry, National Academy of Sciences of Belarus, Kuprevich str., 5/2, 220141 Minsk. khripach@iboch.bas-net.by
authors.forename: Vladimir A
authors.initials: VA
authors.lastname: Khripach
authors.forename: Vladimir N
authors.initials: VN
authors.lastname: Zhabinskii
authors.forename: Anna I
authors.initials: AI
authors.lastname: Kuchto
authors.forename: Galina P
authors.initials: GP
authors.lastname: Fando
authors.forename: Yuliya Y
authors.initials: YY
authors.lastname: Zhiburtovich
authors.forename: Alexander S
authors.initials: AS
authors.lastname: Lyakhov
authors.forename: Alla A
authors.initials: AA
authors.lastname: Govorova
authors.forename: Marinus B
authors.initials: MB
authors.lastname: Groen
authors.forename: Jaap
authors.initials: J
authors.lastname: van der Louw
authors.forename: Aede
authors.initials: A
authors.lastname: de Groot
mesh_terms: D005043:Etiocholanolone / Q000031:analogs & derivatives* / Q000138:chemical synthesis / Q000737:chemistry*; D019811:Hydroxylamine / Q000737:chemistry*; D008958:Models, Molecular; D008968:Molecular Conformation; D012632:Secosteroids / Q000138:chemical synthesis* / Q000737:chemistry; D014961:X-Ray Diffraction
chemical_list: C496276:(13S)-13-iodo-6beta-methoxy-3alpha,5-cyclo-13,14-seco-5alpha-androsta-14,17-dione; D012632:Secosteroids; D019811:Hydroxylamine; D005043:Etiocholanolone