Preparation of optically active allylic hydroperoxy alcohols and 1,3-diols by enzyme-catalyzed kinetic resolution and photooxygenation of chiral homoallylic alcohols

All four possible enantiomers of the 3-hydroperoxy-4-penten-1-ols 2a,b and their corresponding 4-pentene-1,3-diols 4a,b have been prepared for the first time in high enantiomeric purity (up to 98% eel ana in preparative amounts according to two distinct ways: First the photooxygenation of the racemic homoallylic alcohols 1 gave the racemic hydroperoxy alcohols a, which have subsequently been kinetically resolved by horseradish peroxidase (HRP); alternatively, first the lipase-catalyzed resolution afforded the optically active homoallylic alcohols 1 and subsequent photooxygenation led to the enantiomerically enriched hydroperoxy alcohols 2.