New Methods for Synthesis of Bioactive Terpenes

这项研究计划由合成有机 化学课程。 皮尔森博士将开发新的合成 基于过渡金属-烯烃络合物的试剂。 这些 配合物有助于构造复杂的环 现代农业所使用的材料中发现的系统。 这项研究围绕使用聚烯烃-过渡 金属络合物作为反应性中间体用于 季碳中心。 期间制定的方法 这些研究将应用于一些 具有生物活性的萜类天然产物。 环己二烯基铁配合物用于合成 的化合物，如藜芦醇和verrucarol，以及 二萜类化合物stemodinone和aphidicolin的合成。 这些种类化合物中的每一种都显示出抗菌， 抗真菌和/或抗病毒活性。 新发现 二烯基-和二烯铁络合物的反应，其中 侧链烯烃与有机金属单元以 碳-碳键形成过程有待详细研究。 这些和相关的范围和综合应用 将研究反应。 新探 研究紫杉烷衍生物的合成。 这些 化合物，特别是紫杉醇， 抗肿瘤剂。 本文中描述的合成方法 该提案旨在将碳排放的主要部分 通过高度取代的锡烯醇化物的反应 与三羰基（1，3-二甲基-4-甲氧基环己二烯基）铁 六氟磷酸盐，然后进行内部频哪醇反应 来固定八元环

This research program is being funded by the Synthetic Organic Chemistry Program. Dr. Pearson will develop new synthetic reagents based upon transition metal-olefin complexes. These complexes facilitate the construction of complicated ring systems found in the materials used by modern agriculture. This research revolves around the use of polyolefin-transition metal complexes as reactive intermediates for the construction of quaternary carbon centers. The methodology developed during these studies is to be applied in total synthesis of a number of biologically active terpenoid natural products. Cyclohexadienyliron complexes are to be used in the synthesis of trichothecenes such as trichodermol and verrucarol, and in synthesis of the diterpenoids stemodinone and aphidicolin. Each of these classes of compound show antibacterial, antifungal and/or antiviral activity. Newly discovered reactions of dienyl- and diene iron complexes, in which a pendant olefin is coupled to the organometallic unit in a carbon-carbon bond forming process are to be studied in detail. The scope and synthetic applications of these and related reactions will be investigated. A new approach to the synthesis of taxane derivatives will be investigated. These compounds, in particular taxol, show exceptional promise as antitumor agents. The synthetic approach described in this proposal aims to set in place the major part of the carbon skeleton via the reaction of a highly substituted tin enolate with tricarbonyl(l,3-dimethyl-4-methoxycyclohexadienyl)iron hexafluorophosphate, followed by an internal pinacol reaction to set in place the eight-membered ring.