Biosynthetic generation of the species-specific chirality of limonene in Mentha spicata and Citrus unshiu

Abstract

The biosynthetic generation of the species-specific chirality at C-4 of (4S)-(–)- and (4R)-(+) limonenes in Mentha spicata and Citrus unshiu, respectively, is ascribed to the enantiomeric endo-spatial arrangement of linalyl cation intermediates which are both formed by the (2Re,3Si)-face elimination of the diphosphoryl group with respect to the 2(3)-double bond of geranyl diphosphate.