ChemInform Abstract: Synthesis of the Corticoid Side Chain from 17α-(Haloethynyl)-17β-(nitrooxy)androstenes.

ChemInform Abstract

The androstene derivatives (Ia) and (Ib) react according to A) to give the desired products (IIa)-(IId). These are saponified to the alcohols (IIe) and (IIf) which, in turn, are transformed to the acetates (IIg) and (IIh). The ester group in (Ic) can also be eliminated yielding (IIc) albeit only at elevated temperature. The esters (Id), however, do not show any reaction even above 60 °C. The diene (IV) is observed as by-product in the reaction (Ia) (X: -Br) → (IIc) and as main product in the reaction (Ic) → (IIc).