Reaction participants Show >> << Hide
- Name help_outline (2E)-geranyl diphosphate Identifier CHEBI:58057 (Beilstein: 4549979) help_outline Charge -3 Formula C10H17O7P2 InChIKeyhelp_outline GVVPGTZRZFNKDS-JXMROGBWSA-K SMILEShelp_outline CC(C)=CCC\C(C)=C\COP([O-])(=O)OP([O-])([O-])=O 2D coordinates Mol file for the small molecule Search links Involved in 59 reaction(s) Find molecules that contain or resemble this structure Find proteins in UniProtKB for this molecule
- Name help_outline (1R,5R)-β-pinene Identifier CHEBI:50026 Charge 0 Formula C10H16 InChIKeyhelp_outline WTARULDDTDQWMU-RKDXNWHRSA-N SMILEShelp_outline CC1(C)[C@@H]2CCC(=C)[C@H]1C2 2D coordinates Mol file for the small molecule Search links Involved in 1 reaction(s) Find molecules that contain or resemble this structure Find proteins in UniProtKB for this molecule
- Name help_outline diphosphate Identifier CHEBI:33019 (Beilstein: 185088) help_outline Charge -3 Formula HO7P2 InChIKeyhelp_outline XPPKVPWEQAFLFU-UHFFFAOYSA-K SMILEShelp_outline OP([O-])(=O)OP([O-])([O-])=O 2D coordinates Mol file for the small molecule Search links Involved in 1,085 reaction(s) Find molecules that contain or resemble this structure Find proteins in UniProtKB for this molecule
Cross-references
RHEA:32579 | RHEA:32580 | RHEA:32581 | RHEA:32582 | |
---|---|---|---|---|
Reaction direction help_outline | undefined | left-to-right | right-to-left | bidirectional |
UniProtKB help_outline |
|
|||
EC numbers help_outline | ||||
KEGG help_outline | ||||
MetaCyc help_outline |
Related reactions help_outline
More general form(s) of this reaction
Publications
-
Stereochemistry of the proton elimination in the formation of (+)- and (-)-alpha-pinene by monoterpene cyclases from sage (Salvia officinalis).
Pyun H.J., Wagschal K.C., Jung D.I., Coates R.M., Croteau R.
The three pinene synthases (cyclases) from common sage (Salvia officinalis) catalyze the conversion of geranyl pyrophosphate to the bicyclic olefins (+)-alpha-pinene and (+)-camphene (cyclase I), (-)-alpha-pinene, (-)-beta-pinene, and (-)-camphene (cyclase II), and (+)-alpha-pinene and (+)-beta-pi ... >> More
The three pinene synthases (cyclases) from common sage (Salvia officinalis) catalyze the conversion of geranyl pyrophosphate to the bicyclic olefins (+)-alpha-pinene and (+)-camphene (cyclase I), (-)-alpha-pinene, (-)-beta-pinene, and (-)-camphene (cyclase II), and (+)-alpha-pinene and (+)-beta-pinene (cyclase III), in addition to smaller amounts of monocyclic and acyclic monoterpene olefins. (1R)-4-2H1- and (1S)-4-2H1-labeled geranyl pyrophosphates were prepared and used to examine the stereochemistry of the C3-proton elimination from the pinyl cation intermediates in the formation of the alpha-pinene enantiomers. Mass spectrometric analysis of the biosynthetic products derived from the chirally deuterated substrates revealed that cyclase I and cyclase III removed the C4-proR-hydrogen of the substrate (C3 proton trans to the dimethyl bridge of the pinyl nucleus) with a stereoselectivity exceeding 94% in the formation of (+)-alpha-pinene. Similarly, cyclase II removed the C4-proS-hydrogen of the substrate (C3-trans proton of the corresponding pinyl cation) with a stereoselectivity exceeding 78% in the formation of (-)-alpha-pinene. The stereoselectivity of these C3-axial hydrogen eliminations is rationalized on the basis of a stereochemical model for the electrophilic isomerization-cyclization reaction sequence catalyzed by the pinene cyclases. The changes in the overall rates of olefin biosynthesis by these enzymes and in the product ratios resulting from deuterium substitution also permitted confirmation of isotopically sensitive branching in pinene biosynthesis and allowed the observation of primary kinetic isotope effects in isolation. << Less
Arch Biochem Biophys 308:488-496(1994) [PubMed] [EuropePMC]
This publication is cited by 2 other entries.
-
Monoterpene biosynthesis: isotope effects associated with bicyclic olefin formation catalyzed by pinene synthases from sage (Salvia officinalis).
Wagschal K.C., Pyun H.J., Coates R.M., Croteau R.
The three pinene synthases (cyclases) from common sage (Salvia officinalis) catalyze the conversion of geranyl pyrophosphate to the bicyclic olefins (+)-alpha-pinene and (+)-camphene (cyclase I), (-)-alpha-pinene, (-)-beta-pinene, and (-)-camphene (cyclase II), and (+)-alpha-pinene and (+)-beta-pi ... >> More
The three pinene synthases (cyclases) from common sage (Salvia officinalis) catalyze the conversion of geranyl pyrophosphate to the bicyclic olefins (+)-alpha-pinene and (+)-camphene (cyclase I), (-)-alpha-pinene, (-)-beta-pinene, and (-)-camphene (cyclase II), and (+)-alpha-pinene and (+)-beta-pinene (cyclase III), in addition to smaller amounts of monocyclic and acyclic monoterpene olefins. [1-3H,4-2H2]- and [10-2H2]-geranyl pyrophosphates were prepared and used in conjunction with 1-3H- and 1-3H,10-2H3-labeled geranyl precursors to examine the isotope effects attending the C4- and C10-deprotonation steps in the enzymatic synthesis of the pinenes. The observation of isotopically sensitive branching within each set of stereochemically related bicyclic olefins confirmed that each product set was synthesized by the respective pinene synthase by partitioning of common carbocationic intermediates along different reaction channels at the active site. The changes in product distribution resulting from deuterium substitution at C4 and C10 of the substrate were used to determine kinetic isotope effects (KIEs) for the terminating deprotonations; these observed KIEs represent the lower limits of the intrinsic isotope effects. The intramolecular isotope effects for the methyl-methylene elimination in beta-pinene formation by cyclases II and III were also evaluated with [10-2H2]geranyl pyrophosphate as substrate and by MS analysis of the olefin products. The intramolecular KIEs (kH/kD = 3.0 and 3.5) were significantly higher than the observed KIEs determined from product ratios (kH/kD = 1.7 and 2.6) since the former involves considerably less masking of the intrinsic isotope effects. << Less
Arch Biochem Biophys 308:477-487(1994) [PubMed] [EuropePMC]
This publication is cited by 2 other entries.