NEW METHODOLOGY FOR ORGANIC SYNTHESIS

该项目涉及开发一些新的反应， 有机合成的概念 这些研究将包括 潜在的“水”负离子化学和不对称 在Diels-Alder反应中诱导芳烃铬基团。 总 包括受体配体的维生素D衍生物和紫杉醇的合成 将进行。 将开发新的有机硅方法学 涉及TMS组在Claisen重排中的不对称诱导。 烯丙基硅烷的内部活化将被研究。 氧化 硅烷的断裂和氧化自由基加成， 将研究烯丙基硅烷。 最后，光脱羰和 将溶剂分解反应应用于白三烯合成。 尽管我们的主要目标是尽可能地了解 这些新的反应将在以下背景下进行研究： 目前感兴趣的合成问题如维生素D代谢物， 维生素D受体的亲和配体，紫杉醇，紫杉醇的前体 抗体，奎宁，阿曲霉素，recifeifelicine，X-14547 A，tetronomycin， zoapatanol、pinidine、forskolin和白三烯。

This project involves the development of a number of new reactions and concepts for organic synthesis. These will include studies of the potential for "aqueous" pentadienyl anion chemistry and the asymmetric induction of an arene chromium group in the Diels-Alder reaction. Total syntheses of vitamin D derivatives, including receptor ligands, and taxusin will be undertaken. New organosilicon methodology will be developed involving asymmetric induction in Claisen rearrangements by the TMS group. Internal activation of allylsilanes will be studied. The oxidative fragmentation of silanes and the oxidative free-radical addition to allylsilanes will be investigated. Finally, both photodecarbonylation and solvolysis reactions will be applied to leukotriene synthesis. Although the primary goal is to learn all that we can about the reactions in question, these new reactions will be investigated in the context of synthetic problems of current interest such as vitamin D metabolites, affinity ligands for the vitamin D receptor, taxusin, precursors for taxol antibodies, quinine, ajmalicine, recifeiolide, X-14547A, tetronomycin, zoapatanol, pinidine, forskolin, and leukotrienes.