Synthesis of side-chain oxysterols and their enantiomers through cross-metathesis reactions of Δ22 steroids

•Synthesis of oxysterol enantiomers.•Cross-metathesis reactions of Δ22 steroids.•Enantioselective synthesis.

A synthetic route that utilizes a cross-metathesis reaction with Δ22 steroids has been developed to prepare sterols with varying C-27 side-chains. Natural sterols containing hydroxyl groups at the 25 and (25R)-26 positions were prepared. Enantiomers of cholesterol and (3β,25R)-26-hydroxycholesterol (27-hydroxycholesterol) trideuterated at C-19 were prepared for future biological studies.