(-)-alpha-pinene synthase;
(-)-alpha-pinene/(-)-camphene synthase;
(-)-alpha-pinene cyclase

Lyases;
Carbon-oxygen lyases;
Acting on phosphates

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

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

R05765

geranyl diphosphate [CPD:C00341]

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.

1  [PMID:6693393]

Gambliel H, Croteau R

Pinene cyclases I and II. Two enzymes from sage (Salvia officinalis) which catalyze stereospecific cyclizations of geranyl pyrophosphate to monoterpene olefins of opposite configuration.

J. Biol. Chem. 259 (1984) 740-8.

2  [PMID:3314988]

Croteau RB, Wheeler CJ, Cane DE, Ebert R, Ha HJ

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.

Biochemistry. 26 (1987) 5383-9.

3  [PMID:3392006]

Croteau R, Satterwhite DM, Cane DE, Chang CC

Biosynthesis of monoterpenes. Enantioselectivity in the enzymatic cyclization of  (+)- and (-)-linalyl pyrophosphate to (+)- and (-)-pinene and (+)- and (-)-camphene.

J. Biol. Chem. 263 (1988) 10063-71.

4  [PMID:2768265]

Croteau R, Satterwhite DM

Biosynthesis of monoterpenes. Stereochemical implications of acyclic and monocyclic olefin formation by (+)- and (-)-pinene cyclases from sage.

J. Biol. Chem. 264 (1989) 15309-15.

5  [PMID:8109979]

Pyun HJ, Wagschal KC, Jung DI, Coates RM, Croteau R

Stereochemistry of the proton elimination in the formation of (+)- and (-)-alpha-pinene by monoterpene cyclases from sage (Salvia officinalis).

Arch. Biochem. Biophys. 308 (1994) 488-96.

6  [PMID:12226526]

Lu S, Xu R, Jia JW, Pang J, Matsuda SP, Chen XY

Cloning and functional characterization of a beta-pinene synthase from Artemisia  annua that shows a circadian pattern of expression.

Plant. Physiol. 130 (2002) 477-86.

7  [PMID:1731633]

Lewinsohn E, Gijzen M, Croteau R

Wound-inducible pinene cyclase from grand fir: purification, characterization, and renaturation after SDS-PAGE.

Arch. Biochem. Biophys. 293 (1992) 167-73.

8  [PMID:9268308]

Bohlmann J, Steele CL, 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) 21784-92.

9  [PMID:10441373]

Bohlmann J, Phillips M, Ramachandiran V, Katoh S, Croteau R

cDNA cloning, characterization, and functional expression of four new monoterpene synthase members of the Tpsd gene family from grand fir (Abies grandis).

Arch. Biochem. Biophys. 368 (1999) 232-43.

10 [PMID:15978541]

Hyatt DC, 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) 222-33.

11 [PMID:10562434]

Phillips MA, Savage TJ, Croteau R

Monoterpene synthases of loblolly pine (Pinus taeda) produce pinene isomers and enantiomers.

Arch. Biochem. Biophys. 372 (1999) 197-204.

12 [PMID:12623076]

Phillips MA, Wildung MR, Williams DC, Hyatt DC, Croteau R

cDNA isolation, functional expression, and characterization of (+)-alpha-pinene synthase and (-)-alpha-pinene synthase from loblolly pine (Pinus taeda): stereocontrol in pinene biosynthesis.

Arch. Biochem. Biophys. 411 (2003) 267-76.

13 [PMID:12970502]

McKay SA, Hunter WL, Godard KA, Wang SX, Martin DM, Bohlmann J, Plant AL

Insect attack and wounding induce traumatic resin duct development and gene expression of (-)-pinene synthase in Sitka spruce.

Plant. Physiol. 133 (2003) 368-78.

14 [PMID:15921711]

Huber DP, Philippe RN, Godard KA, Sturrock RN, Bohlmann J

Characterization of four terpene synthase cDNAs from methyl jasmonate-induced Douglas-fir, Pseudotsuga menziesii.

Phytochemistry. 66 (2005) 1427-39.