KEGG ENZYME: 4.2.3.119

ENZYME: 4.2.3.119

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

Sysname

geranyl-diphosphate diphosphate-lyase [cyclizing, (-)-alpha-pinene-forming]

Reaction(IUBMB)

geranyl diphosphate = (-)-alpha-pinene + diphosphate [RN:R05765]

Reaction(KEGG)

R05765

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)
DOI:10.1021/bi00391a025

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

[ag:AAB71085]

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

[ag:AAF61455]

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

[ag:AAO61225]

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)
DOI:10.1104/pp.103.022723