Collect. Czech. Chem. Commun. 2001, 66, 1764-1776

Radical Oxidation of 17-Functionalized 14α-Hydroxy Steroids

Vladimir A. Khripacha,*, Vladimir N. Zhabinskiia, Anna I. Kotyatkinaa, Galina P. Fandoa, Yuliya Y. Zhiburtovicha, Alexander S. Lyakhova, Alla A. Govorovaa, Marinus B. Groenb, Jaap van der Louwb and Aede de Grootc

a Institute of Bioorganic Chemistry, National Academy of Sciences of Belarus, Kuprevich Str. 5/2, 220141 Minsk, Belarus
b Scientific Development Group, N. V. Organon, P.O. Box 20, 5340 BH Oss, Netherlands
c Wageningen University, Laboratory of Organic Chemistry, Dreijenplein 8, 6703 HB Wageningen, Netherlands


The radical oxidation of 14α-hydroxy steroids with various functional groups at C-17 was studied. Lead tetraacetate and ceric ammonium nitrate were used as oxidizing agents. It was shown that reactions of this type afforded complex mixtures of compounds. However, the radical oxidation of 14α-hydroxy-17-oxo steroid (lead tetraacetate version of the hypoiodite reaction) proceeded smoothly with formation of the 13,14-secosteroid in up to 85% yield. The structure and conformation of the formed 13α-iodo-3α,5-cyclo-13,14-seco-5α-androst-5-ene-14,17-dione was determined by X-ray analysis.

Keywords: Steroids; Secosteroids; Radical oxidations; Lead tetraacetate; Ceric ammonium nitrate; Fragmentation; Conformation analysis.

References: 15 live references.