Racemization of 6-methoxydihydrosanguinarine in methanol investigated by enantioselective dynamic HPLC

Abstract

A biologically active benzophenanthridine alkaloid, 6-methoxydihydrosanguinarine (MS), was isolated from Hylomecon plants. Although enantiomers of MS can be separated by chiral HPLC, its isomers rapidly form a racemic mixture in methanol. The rate constants for the racemization of MS enantiomers were 9.20 × 10 −4 s −1 and 9.95 × 10 −4 s −1 for (+)-MS and (−)-MS, respectively, as determined by dynamic HPLC and chiral chromatography. This unusually rapid racemization may originate from the formation of a stable iminium ion intermediate, sanguinarine. Therefore, the variety of biological activities exhibited by MS may be attributable to a combination of (+)-MS, (−)-MS, and sanguinarine.