Diterpenoid resin acid biosynthesis in conifers: enzymatic cyclization of geranylgeranyl pyrophosphate to abietadiene, the precursor of abietic acid.
Abietic acid is a major component of the rosin fraction of oleoresin synthesized by conifer species, such as grand fir (Abies grandis) and lodgepole pine (Pinus contorta), as a defensive secretion against insect and pathogen attack. This diterpenoid resin acid is derived from geranylgeranyl pyrophosphate by conversion to abietadiene and sequential oxidation of the C18-methyl group of the precursor olefin to a carboxyl function. Resin acid biosynthesis is constitutively expressed at high levels in lodgepole pine stem and is induced to these levels by stem wounding in grand fir. Soluble enzyme extracts of lodgepole pine stem and of mechanically wounded grand fir stem catalyzed the divalent metal ion-dependent cyclization of [1-3H]geranylgeranyl pyrophosphate to (-)-abieta-7(8),13(14)-diene. The wound-inducible enzyme was partially purified and identified as an 80-kDa protein with general characteristics typical of those of other terpenoid cyclases. Although the enzymatic cyclization sequence almost certainly involves the formation of copalyl pyrophosphate and a pimaradiene as stable intermediates, no evidence for the separation of the corresponding partial activities was obtained. A pathway involving the production of various pimaradiene and abietadiene isomers is proposed to account for the origin of several common resin acids.
LaFever
R E
RE
Institute of Biological Chemistry, Washington State University, Pullman 99164-6340.
Vogel
B S
BS
Croteau
R
R
D045784:Abietanes; D004047:Diethyl Pyrocarbonate / Q000494:pharmacology; D004224:Diterpenes / Q000378:metabolism*; D007535:Isomerases / Q000302:isolation & purification / Q000378:metabolism*; D010616:Phenanthrenes / Q000378:metabolism*; D011106:Polyisoprenyl Phosphates / Q000378:metabolism*; D014197:Trees / Q000378:metabolism*
D045784:Abietanes; D004224:Diterpenes; D010616:Phenanthrenes; D011106:Polyisoprenyl Phosphates; D007535:Isomerases; C088741:abietadiene cyclase; D004047:Diethyl Pyrocarbonate; C002963:geranylgeranyl pyrophosphate; C023710:abietic acid