Monoterpene biosynthesis: demonstration of a geranyl pyrophosphate:sabinene hydrate cyclase in soluble enzyme preparations from sweet marjoram (Majorana hortensis).

@article{Hallahan1988MonoterpeneBD,
  title={Monoterpene biosynthesis: demonstration of a geranyl pyrophosphate:sabinene hydrate cyclase in soluble enzyme preparations from sweet marjoram (Majorana hortensis).},
  author={T. Hallahan and R. Croteau},
  journal={Archives of biochemistry and biophysics},
  year={1988},
  volume={264 2},
  pages={
          618-31
        }
}
A soluble enzyme preparation from the leaves of sweet marjoram (Majorana hortensis Moench) catalyzes the divalent cation-dependent cyclization of [1-3H]geranyl pyrophosphate to the bicyclic monoterpene alcohols (+)-[6-3H]cis- and (+)-[6-3H]-transsabinene hydrate, providing labeling patterns consistent with current mechanistic considerations. No free intermediates were detectable in the conversion of geranyl pyrophosphate to the sabinene hydrates as determined by isotopic dilution experiments… Expand
Monoterpene biosynthesis: mechanism and stereochemistry of the enzymatic cyclization of geranyl pyrophosphate to (+)-cis- and (+)-trans-sabinene hydrate.
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The results define the overall stereochemistry of the coupled isomerization-cyclization to sabinene hydrate, demonstrate the 1,2-hydride shift, and confirm the electrophilic nature of this enzymatic reaction type. Expand
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Characterization and mechanism of (4S)-limonene synthase, a monoterpene cyclase from the glandular trichomes of peppermint (Mentha x piperita).
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Experiments with alternate substrates and substrate analogs confirmed many elements of the proposed reaction mechanism, including the binding of geranyl pyrophosphate in the form of a complex with the divalent metal ion, the preliminary isomerization of gerANY to linalyl pyroph phosphate (a bound intermediate capable of cyclization), and the participation of a series of carbocation:pyrophosphates anion pairs in the reaction sequence. Expand
Stereochemical mechanism of two sabinene hydrate synthases forming antipodal monoterpenes in thyme (Thymus vulgaris).
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It is revealed that the stereospecificity of TPS6 and TPS7 is determined by the formation of the first intermediate, linalyl diphosphate, and the influence of this amino acid residue on the reaction mechanism is discussed. Expand
Advances in the Enzymology of Monoterpene Cyclization Reactions
Monoterpene cyclases catalyze the electrophilic isomerization–cyclization of the C10 prenyl diphosphate, geranyl diphosphate (GPP), to generate a diverse selection of monoterpenes. This tightlyExpand
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The monoterpene cyclase, gamma-terpinene synthase, from Thymus vulgaris (thyme) leaves was purified to apparent homogeneity by isoelectric focusing and dye-ligand, anion-exchange, hydrophobicExpand
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Distribution of the cis-sabinene hydrate acetate-chemotype in accessions of marjoram (Origanum majorana L.)
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If further sensorial studies can give leads as to which of the two compounds contributes to the preferred flavor, the variation observed among natural populations could be used in breeding towards an optimized quality of marjoram. Expand
Comparison of Two Monoterpene Cyclases Isolated from Higher Plants; γ-Terpinene Synthase from Thymus Vulgaris, and Limonene Synthase from Mentha x Piperita
Monoterpenes are the C10 members of the terpenoid family of natural products, and they diverge from higher isoprenoid biosynthesis at the level of geranyl pyrophosphate. γ-Terpinene synthase andExpand
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