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.
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.
Khripach
Vladimir A
VA
Institute of Bioorganic Chemistry, National Academy of Sciences of Belarus, Kuprevich str., 5/2, 220141 Minsk. khripach@iboch.bas-net.by
Zhabinskii
Vladimir N
VN
Kuchto
Anna I
AI
Fando
Galina P
GP
Zhiburtovich
Yuliya Y
YY
Lyakhov
Alexander S
AS
Govorova
Alla A
AA
Groen
Marinus B
MB
van der Louw
Jaap
J
de Groot
Aede
A
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
C496276:(13S)-13-iodo-6beta-methoxy-3alpha,5-cyclo-13,14-seco-5alpha-androsta-14,17-dione; D012632:Secosteroids; D019811:Hydroxylamine; D005043:Etiocholanolone