Reaction: geranyl diphosphate = (–)-β-pinene + diphosphate
For diagram of reaction click here.
Glossary: (–)-β-pinene = (1S,5S)-6,6-dimethyl-2-methylenebicyclo[3.1.1]hept-2-ene
Other name(s): β-geraniolene synthase; (–)-(1S,5S)-pinene synthase; geranyldiphosphate diphosphate lyase (pinene forming)
Systematic name: geranyl-diphosphate diphosphate-lyase [cyclizing, (–)-β-pinene-forming]
Comments: Cyclase II of Salvia officinalis (sage) produces about equal parts (–)-α-pinene, (–)-β-pinene and (–)-camphene, plus traces of other monoterpenoids. The enzyme, which requires Mg2+ (preferred to Mn2+), can also use (3S)-Linalyl diphosphate (preferred to (3R)-linalyl diphosphate) [1-4]. The enzyme from Abies grandis (grand fir) produces roughly equal parts of (–)-α-pinene and (–)-β-pinene [6-9]. Cyclase IV from Pinus contorta (lodgepole pine) produces 63% (–)-β-pinene, 26% 3-carene, and traces of α-pinene [10]. Synthase III from Pinus taeda (loblolly pine) forms (–)-β-pinene with traces of α-pinene and requires Mn2+ and K+ (Mg2+ is ineffective) [11]. A cloned enzyme from Artemisia annua (sweet wormwood) gave (–)-β-pinene with traces of (–)-α-pinene [5]. The enzyme from Picea sitchensis (Sika spruce) forms 30% (–)-β-pinene and 70% (–)-α-pinene [12]. See also EC 4.2.3.119, (–)-α-pinene synthase, EC 4.2.3.117, (–)-camphene synthase, and EC 4.2.3.107 (+)-3-carene synthase.
Links to other databases: BRENDA, EXPASY, KEGG, Metacyc, CAS registry number:
References:
1. Croteau, R.B., Wheeler, C.J., Cane, D.E., Ebert, R. and Ha, H.J. Isotopically sensitive branching in the formation of cyclic monoterpenes: proof that (–)-α-pinene and (–)-β-pinene are synthesized by the same monoterpene cyclase via deprotonation of a common intermediate. Biochemistry 26 (1987) 5383-5389. [PMID: 3314988]
2. Croteau, R. and Satterwhite, D.M. Biosynthesis of monoterpenes. Stereochemical implications of acyclic and monocyclic olefin formation by (+)- and (–)-pinene cyclases from sage. J. Biol. Chem. 264 (1989) 15309-15315. [PMID: 2768265]
3. Croteau, R., Satterwhite, D.M., Cane, D.E. and Chang, C.C. Biosynthesis of monoterpenes. Enantioselectivity in the enzymatic cyclization of (+)- and (–)-linalyl pyrophosphate to (+)- and (–)-pinene and (+)- and (–)-camphene. J. Biol. Chem. 263 (1988) 10063-10071. [PMID: 3392006]
4. Pyun, H.J., Wagschal, K.C., Jung, D.I., Coates, R.M. and Croteau, R. Stereochemistry of the proton elimination in the formation of (+)- and (–)-α-pinene by monoterpene cyclases from sage (Salvia officinalis). Arch. Biochem. Biophys. 308 (1994) 488-496. [PMID: 8109979]
5. Lu, S., Xu, R., Jia, J.W., Pang, J., Matsuda, S.P. and Chen, X.Y. Cloning and functional characterization of a β-pinene synthase from Artemisia annua that shows a circadian pattern of expression. Plant Physiol. 130 (2002) 477-486. [PMID: 12226526]
6. Gijzen, M., Lewinsohn, E. and Croteau, R. Characterization of the constitutive and wound-inducible monoterpene cyclases of grand fir (Abies grandis). Arch. Biochem. Biophys. 289 (1991) 267-273. [PMID: 1898071]
7. Lewinsohn, E., Gijzen, M. and Croteau, R. Wound-inducible pinene cyclase from grand fir: purification, characterization, and renaturation after SDS-PAGE. Arch. Biochem. Biophys. 293 (1992) 167-173. [PMID: 1731633]
8. Bohlmann, J., Steele, C.L. and Croteau, R. Monoterpene synthases from grand fir (Abies grandis). cDNA isolation, characterization, and functional expression of myrcene synthase, (–)-(4S)-limonene synthase, and (–)-(1S,5S)-pinene synthase. J. Biol. Chem. 272 (1997) 21784-21792. [PMID: 9268308]
9. Hyatt, D.C. and Croteau, R. Mutational analysis of a monoterpene synthase reaction: altered catalysis through directed mutagenesis of (–)-pinene synthase from Abies grandis. Arch. Biochem. Biophys. 439 (2005) 222-233. [PMID: 15978541]
10. Savage, T.J., Ichii, H., Hume, S.D., Little, D.B. and Croteau, R. Monoterpene synthases from gymnosperms and angiosperms: stereospecificity and inactivation by cysteinyl- and arginyl-directed modifying reagents. Arch. Biochem. Biophys. 320 (1995) 257-265. [PMID: 7625832]
11. Phillips, M.A., Savage, T.J. and Croteau, R. Monoterpene synthases of loblolly pine (Pinus taeda) produce pinene isomers and enantiomers. Arch. Biochem. Biophys. 372 (1999) 197-204. [PMID: 10562434]
12. McKay, S.A., Hunter, W.L., Godard, K.A., Wang, S.X., Martin, D.M., Bohlmann, J. and Plant, A.L. Insect attack and wounding induce traumatic resin duct development and gene expression of (–)-pinene synthase in Sitka spruce. Plant Physiol. 133 (2003) 368-378. [PMID: 12970502]