Perez A L, Gries R, Gries G, Oehlschlager A C
Department of Chemistry, Simon Fraser University, Burnaby, British Columbia, Canada.
Bioorg Med Chem. 1996 Mar;4(3):445-50. doi: 10.1016/0968-0896(96)00024-7.
(Z)-6-Nonen-2-one (1) has recently been shown to be the biosynthetic precursor for the aggregation pheromone exo-brevicomin (2) in mountain pine beetle (MPB) males, Dendroctonus ponderosae (Hopkins). We tested the hypotheses that (1) 6-methyl-6-hepten-2-one (3) is the biosynthetic precursor for the aggregation pheromone frontalin (4) in the spruce beetle (SB), Dendroctonus rufipennis (Kirby), and (2) that frontalin and exo-brevicomin are produced from 3 and 1, respectively, only by beetles that utilize them as aggregation pheromones. Exposure of scolytids MPB, SB, pine engraver (PE), Ips pini (Say) and Ips tridens (Mannerheim) and West Indian sugar cane weevil (WISW), Metamasius hemipterus sericeus (Olivier) to deuterio- or protio-3 invariably resulted in the production of deuterio- or protio-4. Similarly, exposure of SB, WISW and I. tridens to 1 resulted in the production of 2. We were unable to demonstrate the presence of 3 in SB volatiles, nor were we able to demonstrate the conversion of 6-methyl-5-hepten-2-one to 3 by SB. Production of enantiomerically enriched frontalin and exo-brevicomin by all the beetles exposed to respective precursors reveals widespread occurrence of nonspecific polysubstrate monooxidases in the Coleoptera.
（Z）-6-壬烯-2-酮（1）最近被证明是山松甲虫（MPB）雄性，即西松大小蠹（霍普金斯）聚集信息素外-短叶松素（2）的生物合成前体。我们测试了以下假设：（1）6-甲基-6-庚烯-2-酮（3）是云杉小蠹（SB），即红翅大小蠹（柯比）聚集信息素frontalin（4）的生物合成前体；（2）frontalin和外-短叶松素分别仅由将它们用作聚集信息素的甲虫从3和1产生。将小蠹科昆虫MPB、SB、松树小蠹（PE）、松果梢斑螟（赛）和三叉梢斑螟（曼纳海姆）以及西印度甘蔗象鼻虫（WISW），即半翅蔗象（奥利弗）暴露于氘代或普通的3，总是会产生氘代或普通的4。同样，将SB、WISW和三叉梢斑螟暴露于1会产生2。我们无法证明SB挥发物中存在3，也无法证明SB能将6-甲基-5-庚烯-2-酮转化为3。所有暴露于各自前体的甲虫产生对映体富集的frontalin和外-短叶松素，这表明鞘翅目中广泛存在非特异性多底物单氧化酶。
