Biosynthesis of Cyclic Monoterpenoids. Involvement of Stereochemically Specified Linalyl Cation in the Cyclization of C10-Prenyl Chain
- 5 January 1988
- journal article
- research article
- Published by Oxford University Press (OUP) in Chemistry Letters
- Vol. 17 (1) , 115-118
- https://doi.org/10.1246/cl.1988.115
Abstract
Incubation of geranyl diphosphate (GPP) and the enantiomers and racemate of linalyl diphosphate (LPP) with the limonene synthetase isolated from Mentha spicata resulted in the conversion of GPP and (S)-LPP into (S)-limonene; this can be taken as evidence that linalyl cation having not only the (S)-LPP-like configuration but also C-1 and C-6 double bonds situated in the anti spatial arrangement is involved in the process of the cyclization of GPP to (S)-limonene. The intermediacy of the linalyl cation was supported by the evaluation of the potential energy of the cation with the MO calculation.Keywords
This publication has 11 references indexed in Scilit:
- Interconversion and cyclization of acyclic allylic pyrophosphates in the biosynthesis of cyclic monoterpenoids in higher plantsPhytochemistry, 1986
- [15] Synthesis of allylic and homoallylic isoprenoid pyrophosphatesPublished by Elsevier ,1985
- Metabolism of linaloyl, neryl and geranyl pyrophosphates in Artemisia annuaPhytochemistry, 1983
- Studies on the biosynthesis of the carane skeletonPhytochemistry, 1980
- Biosynthesis of monoterpenes: Preliminary characterization of bornyl pyrophosphate synthetase from sage (Salvia officinalis) and demonstration that geranyl pyrophosphate is the preferred substrate for cyclizationArchives of Biochemistry and Biophysics, 1979
- Electronic structures of polymers using the tight-binding approximation. III. Density matrix approach to poly-L-alanine and polyglycine-water complex by the CNDO/2 methodThe Journal of Chemical Physics, 1974
- The metabolism of linalool in Citrus plantsPhytochemistry, 1969
- Terpene biosynthesis: Utilization of neryl pyrophosphate by an enzyme system from Pinus radiata seedlingsArchives of Biochemistry and Biophysics, 1969
- Molecular orbital theory of the electronic structure of organic compounds. I. Substituent effects and dipole momentsJournal of the American Chemical Society, 1967
- Synthese von Geranyl‐ und Farnesyl‐pyrophosphatAngewandte Chemie, 1959