RADICAL MEDIATED CYCLIZATION REACTIONS

许多治疗上重要的天然产物和药剂 可以由官能化的环戊烷和二氧戊环衍生物制备。 继续制定高效率和高效率的 提出了这些环系统的立体选择性合成。 这 方法学是基于自由基介导的添加 官能化的烯烃或相关物质穿过碳-碳键， 适当活化的乙烯基环丙烷，直接得到环戊烷 单位 重点放在提高目前的数字化水平， 立体选择性和对映选择性。 此夕h 新型自由基加成/异构化反应的发展 用于构建高度官能化的环戊醇物质的方法是 计划好了 最后，非对映选择性远程（γ）官能化 将探索仲醇。 抗肿瘤抗生素Brefeldin A的合成及抗白血病药物的研究 试剂罗格列胺，其各自利用环-葡糖苷酸的分子内变体， 五角大楼将进行调查。 成功完成 这些合成将以最有效的方式提供靶（或类似物 到目前为止的方式。

Many therapeutically important natural products and pharmaceutical agents can be prepared from functionalized cyclopentane and dioxolane derivatives. The continued development of methodology for the efficient and stereoselective synthesis of these ring systems is proposed. This methodology is based on the free radical mediated addition of functionalized olefins or related species across the carbon-carbon bond of suitably activated vinylcyclopropanes to afford directly the cyclopentane units. Emphasis is placed on enhancing current levels of dia- stereoselectivity and enantioselectivity upon bond formation. Further, the development of novel free radical-based annelation/isomerization reactions for the construction of highly functionalized cyclopentanol species is planned. Finally, diastereoselective remote (Gamma) functionalization of secondary alcohols will be explored. Syntheses of the antitumor antibiotic brefeldin A and The antileukemic agent rocaglamide, which each utilize intramolecular variants of the cyclo- pentannelation process, will be investigated. Successful completion of these syntheses will afford the targets (or analogs) in the most efficient manner to date.