Complexes of bivalent cations with neryl and geranyl pyrophosphate: Their role in terpene biosynthesis

Abstract

Kinetic analysis of the nonenzymic solvolysis of neryl and geranyl pyrophosphate (NPP and GPP, respectively) showed that the dissociation constants of the bis-metallic complexes with Mg2+ and Mn2+ were larger for NPP than for GPP by approximately one order of magnitude. Rate constants for reaction of the bis-metallic complexes were larger for NPP than for GPP. Qualitatively similar behavior was observed with complexes of Co2+. Extents of elimination and cyclization were increased by metal ions. Carbocyclase-catalyzed formation of cyclic monoterpene hydrocarbons in the presence of Mg2+ involved bis-metallic complexes as the "true" substrates. © 1984.