Methods were developed and optimized for the preparation of the 2,3-cis- and the 10,11-cis-isomers of silybin by the Lewis acid catalyzed (BF3∙OEt2) isomerization of silybins A (1a) and B (1b) (trans-isomers). The absolute configuration of all optically pure compounds was determined by using NMR and comparing their electronic circular dichroism data with model compounds of known absolute configurations. Mechanisms for cis-trans-isomerization of silybin are proposed and supported by quantum mechanical calculations.

Department of Biochemistry Faculty of Science Charles University Prague Hlavova 8 CZ 12840 Prague 2 Czech Republic

Department of Physical Chemistry University of Olomouc tř 17 listopadu 12 CZ 77146 Olomouc Czech Republic

Inserm UMR S850 Faculté de Pharmacie Université de Limoges 2 Rue du Docteur Marcland F 87025 Limoges France

Institute of Microbiology v v i AS CR Vídeňská 1083 Prague 4 CZ 14220 Czech Republic

Institute of Organic Chemistry and Biochemistry v v i AS CR Flemingovo náměstí 2 Prague 6 CZ 16610 Czech Republic

Laboratoire de Chimie des Matériaux Nouveaux Université de Mons Place du Parc 20 B 7000 Mons Belgium

Present address Department of Physics Chemistry and Biology Linköping University SE 58183 Linköping Sweden

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