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

Khripach, V.A.
Zhabinskii, V.N.
Kuchto, A.I.
Fando, G.P.
Zhiburtovich, Y.Y.
Lyakhov, A.S.
Govorova, A.A.
Groen, M.B.
Louw, van der, J.
Groot, de, Æ.

Open link

Publication date

January 2004

DOI

10.1016/j.steroids.2004.04.006

Publisher

Elsevier BV

Abstract

The synthesis of 13,14-seco steroids starting from easily available (13S)-13-iodo-6-methoxy-3,5-cyclo-13,14-seco-5-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