Norrish-Prins reaction as a key step in the synthesis of 14β-hydroxy-5α (or 5β or Δ5,6)-pregnane derivatives

► Numerous bioactive glycosteroids are characterized by aglycones bearing a 14β-hydroxy pregnane skeleton. ► We disclose in this report the use of Norrish type I-Prins reactions to synthesize 14β-hydroxy pregnane derivatives. ► These studies showed that the A/B ring junction has little influence on the Norrish type I-Prins reaction but that the substitution pattern at position 20 is important. ► The presence of a dioxolane group induced not only the formation of the desired 14β-hydroxy pregnane derivatives in the highest yields but also the formation of new spiro derivatives.