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

鳞翅目昆虫性信息素已被应用于害虫综合治理中，作为害虫监测工具和大规模诱捕的诱饵。此外，雌性和雄性之间的化学通讯中断可能是通过用合成信息素渗透田地来进行的。迄今为止，已确定了500多种蛾类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如尺蛾科中的物种中鉴定出许多环氧烯基化合物。由于环氧信息素包含手性中心，并且仅通过有机反应不容易大规模制备它们，因此环氧信息素作为交配破坏剂的应用非常有限。为了实现一种简便、大量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，除了可以由具有同共轭多烯体系的亚麻酸和亚油酸衍生的环氧信息素外，包括额外的共轭多烯体系的烯烃及其环氧衍生物已被鉴定为天然信息素。因此，我们筛选了200多个微生物检查环氧化，羟基化和去饱和周围的酸和多不饱和烃，环氧信息素的生物合成前体的同共轭多烯系统的能力。结果表明，可以成功地筛选出一些菌株，对其生物转化进行详细的研究。我们现在检查最佳孵育条件以确认代谢物的结构。此外，新的化合物中检测到的产品，我们合成了它们使用乙炔偶联反应。使用合成标准品，通过GC/MS和LC/MS重新检查培养基。

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.