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Keywords:

  • acid-catalyzed rearrangement;
  • carbocations;
  • Lewis acids;
  • pregn-4-en-3β,17α,20β-triol;
  • sterol dehydration;
  • Δ3,5-steradienes;
  • 17,20-diols;
  • 3-hydroxy steroids

The acid-catalyzed dehydration is one of the most important processes, which transforms 3-hydroxy steroids into their corresponding unsaturated derivatives. This reaction is of great importance because it can produce molecules that play a key role in the understanding of the natural metabolism of steroids. Sterol dehydration is generally performed with aqueous acidic systems, and the treatment often affords low yields of the desired compounds and/or complex mixtures of by-products. In this paper, we report the results obtained from the study of the structural and stereochemical effects of the acid-induced reaction of pregn-4-en-3β,17α,20β-triol in anhydrous systems. In particular, the treatment of this trihydroxy steroid model with Lewis acids leads to the corresponding Δ3,5-steradiene as the only product and in very high yields. With Lewis acids, no modifications of the 1,2-diol function on the D-ring are observed, even when the reactions are performed at high temperatures. Protic acid catalysis in non-aqueous organic solvents causes the formation of an epimeric mixture of the corresponding Δ3,5-steradiene derivatives by a partial stereochemical inversion of the asymmetric C-17. The reactivity of the 17α,20β-diolic residue is also evaluated by exposing pregn-4-en-3β,17α,20β-triol and the corresponding Δ3,5-steradiene to the prolonged action of anhydrous protic acid systems under thermal conditions.