Substituted 16α,17α-Cyclohexanopregnanes: the Anionic Oxy-Cope Rearrangement of 3β-Tert-Butyldimethylsilyloxy-19-Hydroxy-19-Vinyl-16α,17α-Cyclohexapregn-5-en-20-One

I. S. Levina^1 #, L. E. Kulikova¹, A. S. Shashkov¹, T. N. Galakhova¹ and A. V. Kamernitsky¹

^#Phone: (495) 137-73-31; e-mail: li@ioc.ac.ru

¹Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninskii pr. 47, Moscow, 119991, Russia

Received: June  20, 2006: in final form: June  26, 2006

Abstract.  (19R)-and (19S)-tert-Butyldimethylsilyl (TBS) ethers of 19-hydroxy-19-vinyl-16α,17α-cyclohexanopregn-5-en-20-ones were synthesized. These compounds containing the 1,5-oxydienoic motif were subjectedto the anionic oxy-Cope rearrangement to obtain 3β-TBS ether of 6β-(3-oxopropyl)-16α,17α-cyclohexano-19-norpregn-5(10)-en-20-one. The structures of the compounds synthesized were confirmed by the analysis of their ¹H and ¹³C NMR spectra.

Key words:  oxy-Cope rearrangement, steroids, pentaranes, NMR spectroscopy

Russian Journal of Bioorganic Chemistry 2007, 33 (3): 310-314