Large-Scale Preparation of Optically Active Lepidopteran Sex Pheromones Using Bio-Conversion

鳞翅目性信息素已被应用于IPM项目中，作为监测工具和大规模诱捕的诱饵。此外，雌性和雄性之间化学交流的中断可能是通过在田野中渗透合成信息素来实现的。到目前为止，已测定了500多种雌蛾信息素的化学结构。虽然它们通常由伯醇及其衍生物组成，但最近从高度进化的昆虫中发现了许多环氧烯基化合物，如尺蛾科的物种。由于环氧类信息素中含有手性中心，仅通过有机反应难以大规模制备，因此环氧类信息素作为交配干扰剂的应用受到很大限制。为了实现一种简单而丰富的合成手性环氧化合物的方法，我们试图寻找能够直接引入手性中心或产生适当中间体的微生物。除了可以从亚麻酸和亚油酸与均共轭多烯体系衍生的环氧类信息素外，烯烃及其包括额外共轭多烯体系的环氧衍生物已被鉴定为一种天然信息素。因此，我们围绕环氧信息素的生物合成前体酸和多不饱和烃的共轭多烯体系，筛选了200多种微生物对环氧化、羟化和脱饱和度的检测能力。因此，可以成功地选择一些菌株对其进行详细的生物转化研究。我们现在正在研究最佳的培养条件，以确认代谢物的结构。此外，在产物中检测到了新的化合物，并通过二烯偶联反应合成了它们。根据合成的标准，正在用GC/MS和LC/MS对培养基复检。

Lepidopteran sex pheromones have been applied in IPM programs as a monitoring tool and a lure for mass trapping. Furthermore, the disruption of the chemical communication between females and males is possibly carried out by permeating a field with synthetic pheromones. Up to date, chemical structures of the pheromones have been determined for the female moths of more than 500 species. While they are usually composed of primary alcohols and their derivative, many epoxyalkenyl compounds were recently identified from highly evolved insects such as species in the family of Geometridae. Since the epoxy pheromones include chiral centers and it is not easy to prepare them in a large scale only by organic reactions, application of the epoxy pheromones as a mating disruptant is very limited. In order to accomplish a method to synthesize the chiral epoxy compounds easily and abundantly, we tried to find microorganisms which have an ability to introduce a chiral center directly or to produce an appropriate intermediate.In addition to the epoxy pheromones, which can be derived from linolenic and linolic acids with a homoconjugated polyene system, alkenes and their epoxy derivatives including an extra conjugated polyene system have been identified as a natural pheromone. Therefore, we screened more than 200 imcroorganisms checking abilities for epoxydation, hydroxylation, and desaturatkm around the homocnjugated polyene system of the acids and poly unsaturated hydrocarbons, biosynthetic precursors of epoxy pheromones. As a result, some strains could be successfully selected to study their bioconversion in detailed. We are now examined the optimum incubation condition to confirm the structures of metabolites. Furthermore, novel compounds were detected among the products and we synthesized them using an acelylenic coupling reaction. With the synthetic standards, culture mediums are being reexamining by GC/MS and LC/MS.