KEGG   ENZYME: 4.2.3.119Help
Entry
EC 4.2.3.119                Enzyme                                 

Name
(-)-alpha-pinene synthase;
(-)-alpha-pinene/(-)-camphene synthase;
(-)-alpha-pinene cyclase
Class
Lyases;
Carbon-oxygen lyases;
Acting on phosphates
BRITE hierarchy
Sysname
geranyl-diphosphate diphosphate-lyase [cyclizing, (-)-alpha-pinene-forming]
Reaction(IUBMB)
geranyl diphosphate = (-)-alpha-pinene + diphosphate [RN:R05765]
Reaction(KEGG)
Substrate
geranyl diphosphate [CPD:C00341]
Product
(-)-alpha-pinene [CPD:C06308];
diphosphate [CPD:C00013]
Comment
Cyclase II of Salvia officinalis (sage) gives about equal parts (-)-alpha-pinene, (-)-beta-pinene and (-)-camphene, plus traces of other monoterpenoids. (3S)-Linalyl diphosphate can also be used by the enzyme in preference to (3R)-linalyl diphosphate. The 4-pro-S-hydrogen of geranyl diphosphate is lost. Requires Mg2+ (preferred to Mn2+) [1-6]. The enzyme from Abies grandis (grand fir) gives roughly equal parts (-)-alpha-pinene and (-)-beta-pinene. However the clone ag11 gave 35% (-)-limonene, 24% (-)-alpha-pinene and 20% (-)-beta-phellandrene. It requires Mn2+ and K+ (Mg2+ is ineffective) [7-10]. Synthase I from Pinus taeda (loblolly pine) produces (-)-alpha-pinene with traces of (-)-beta-pinene and requires Mn2+ (preferred to Mg2+) [11,12]. The enzyme from Picea sitchensis (Sika spruce) forms 70% (-)-alpha-pinene and 30% (-)-beta-pinene [13]. The recombinant PmeTPS1 enzyme from Pseudotsuga menziesii (Douglas fir) gave roughly equal proportions of (-)-alpha-pinene and (-)-camphene plus traces of other monoterpenoids [14]. See also EC 4.2.3.120, (-)-beta-pinene synthase; EC 4.2.3.117, (-)-camphene synthase; EC 4.2.3.16, (-)-limonene synthase; and EC 4.2.3.52, (-)-beta-phellandrene synthase.
History
EC 4.2.3.119 created 2012
Pathway
ec00902  Monoterpenoid biosynthesis
ec01100  Metabolic pathways
ec01110  Biosynthesis of secondary metabolites
Orthology
K07384  (-)-alpha/(-)-beta-pinene synthase
Reference
1  [PMID:6693393]
  Authors
Gambliel H, Croteau R
  Title
Pinene cyclases I and II. Two enzymes from sage (Salvia officinalis) which catalyze stereospecific cyclizations of geranyl pyrophosphate to monoterpene olefins of opposite configuration.
  Journal
J Biol Chem 259:740-8 (1984)
Reference
2  [PMID:3314988]
  Authors
Croteau RB, Wheeler CJ, Cane DE, Ebert R, Ha HJ
  Title
Isotopically sensitive branching in the formation of cyclic monoterpenes: proof that (-)-alpha-pinene and (-)-beta-pinene are synthesized by the same monoterpene cyclase via deprotonation of a common intermediate.
  Journal
Biochemistry 26:5383-9 (1987)
Reference
3  [PMID:3392006]
  Authors
Croteau R, Satterwhite DM, Cane DE, Chang CC
  Title
Biosynthesis of monoterpenes. Enantioselectivity in the enzymatic cyclization of  (+)- and (-)-linalyl pyrophosphate to (+)- and (-)-pinene and (+)- and (-)-camphene.
  Journal
J Biol Chem 263:10063-71 (1988)
Reference
4  [PMID:2768265]
  Authors
Croteau R, Satterwhite DM
  Title
Biosynthesis of monoterpenes. Stereochemical implications of acyclic and monocyclic olefin formation by (+)- and (-)-pinene cyclases from sage.
  Journal
J Biol Chem 264:15309-15 (1989)
Reference
5  [PMID:8109979]
  Authors
Pyun HJ, Wagschal KC, Jung DI, Coates RM, Croteau R
  Title
Stereochemistry of the proton elimination in the formation of (+)- and (-)-alpha-pinene by monoterpene cyclases from sage (Salvia officinalis).
  Journal
Arch Biochem Biophys 308:488-96 (1994)
DOI:10.1006/abbi.1994.1069
Reference
6  [PMID:12226526]
  Authors
Lu S, Xu R, Jia JW, Pang J, Matsuda SP, Chen XY
  Title
Cloning and functional characterization of a beta-pinene synthase from Artemisia  annua that shows a circadian pattern of expression.
  Journal
Plant Physiol 130:477-86 (2002)
DOI:10.1104/pp.006544
Reference
7  [PMID:1731633]
  Authors
Lewinsohn E, Gijzen M, Croteau R
  Title
Wound-inducible pinene cyclase from grand fir: purification, characterization, and renaturation after SDS-PAGE.
  Journal
Arch Biochem Biophys 293:167-73 (1992)
DOI:10.1016/0003-9861(92)90380-F
Reference
8  [PMID:9268308]
  Authors
Bohlmann J, Steele CL, Croteau R.
  Title
Monoterpene synthases from grand fir (Abies grandis). cDNA isolation, characterization, and functional expression of myrcene synthase, (-)-(4S)-limonene synthase, and (-)-(1S,5S)-pinene synthase.
  Journal
J Biol Chem 272:21784-92 (1997)
DOI:10.1074/jbc.272.35.21784
  Sequence
Reference
9  [PMID:10441373]
  Authors
Bohlmann J, Phillips M, Ramachandiran V, Katoh S, Croteau R
  Title
cDNA cloning, characterization, and functional expression of four new monoterpene synthase members of the Tpsd gene family from grand fir (Abies grandis).
  Journal
Arch Biochem Biophys 368:232-43 (1999)
DOI:10.1006/abbi.1999.1332
  Sequence
Reference
10 [PMID:15978541]
  Authors
Hyatt DC, Croteau R
  Title
Mutational analysis of a monoterpene synthase reaction: altered catalysis through directed mutagenesis of (-)-pinene synthase from Abies grandis.
  Journal
Arch Biochem Biophys 439:222-33 (2005)
DOI:10.1016/j.abb.2005.05.017
Reference
11 [PMID:10562434]
  Authors
Phillips MA, Savage TJ, Croteau R
  Title
Monoterpene synthases of loblolly pine (Pinus taeda) produce pinene isomers and enantiomers.
  Journal
Arch Biochem Biophys 372:197-204 (1999)
DOI:10.1006/abbi.1999.1467
Reference
12 [PMID:12623076]
  Authors
Phillips MA, Wildung MR, Williams DC, Hyatt DC, Croteau R
  Title
cDNA isolation, functional expression, and characterization of (+)-alpha-pinene synthase and (-)-alpha-pinene synthase from loblolly pine (Pinus taeda): stereocontrol in pinene biosynthesis.
  Journal
Arch Biochem Biophys 411:267-76 (2003)
DOI:10.1016/S0003-9861(02)00746-4
  Sequence
Reference
13 [PMID:12970502]
  Authors
McKay SA, Hunter WL, Godard KA, Wang SX, Martin DM, Bohlmann J, Plant AL
  Title
Insect attack and wounding induce traumatic resin duct development and gene expression of (-)-pinene synthase in Sitka spruce.
  Journal
Plant Physiol 133:368-78 (2003)
  Sequence
Reference
14 [PMID:15921711]
  Authors
Huber DP, Philippe RN, Godard KA, Sturrock RN, Bohlmann J
  Title
Characterization of four terpene synthase cDNAs from methyl jasmonate-induced Douglas-fir, Pseudotsuga menziesii.
  Journal
Phytochemistry 66:1427-39 (2005)
DOI:10.1016/j.phytochem.2005.04.030
Other DBs
ExplorEnz - The Enzyme Database: 4.2.3.119
IUBMB Enzyme Nomenclature: 4.2.3.119
ExPASy - ENZYME nomenclature database: 4.2.3.119
BRENDA, the Enzyme Database: 4.2.3.119

DBGET integrated database retrieval system