Chlorination of 3β-hydroxyl-5-Δ steroids with anhydrous ferric chloride

Treatment of 3β-hydroxyl-5-Δ steroids with anhydrous FeCl3 in CH2Cl2 afforded reasonable yields of the corresponding alkyl chlorides with a retention of configurations. The structures of the chlorine-exchanging products were determined by NMR and HRMS spectra. The absolute configurations were confirmed by X-ray crystal analysis of 3β-chloro-androst-5-en-17-one. The generality and scope of the reaction were also investigated.