CONFIGURATIONAL ASSIGNMENT OF OPTICALLY-ACTIVE HYDROPEROXY HOMOALLYLIC ALCOHOLS AND THE CORRESPONDING DIOLS BY CIRCULAR-DICHROISM AND MULTIDIMENSIONAL GAS-CHROMATOGRAPHY

Allylic hydroperoxides are a class of compounds of versatile synthetic utility. Optically active diastereomeric hydroperoxy homoallylic alco hols and their corresponding diols are easily available through horser adish peroxidase (HRP)-catalyzed kinetic resolution of racemic hydrope roxides. Here we describe the assignment of the absolute configuration of the optically active products and substrates obtained after HRP-ca talysis by the circular dichroism exciton chirality method. Moreover, the analytical-scale separation of the enantiomers based on multidimen sional gas chromatography on chiral columns is presented. Since the en antiomeric elution order on the ciral columns was constituted, the abs olute stereochemistry of optically active allylic diols can easily be deduced by their retention times on beta-cyclodextrins. (C) 1997 Wiley -Liss, Inc.