ARENE ACTIVATION BY TRANSITION METALS

这项提议的广泛、长期目标是开发应用程序 芳烃-金属pi络合物对总合成的挑战 作为重要天然产物成分的分子阵列 分子，并开发不对称合成的新方法 基于手性辅助导向的芳烃金属亲核加成反应 复合体。 针对以下申请的调查将继续进行 芳烃-锰三甲酰基和芳烃(环戊二烯基)Ru 合成瑞斯托菌素A中的阳离子，这是一种复杂的糖肽 与万古霉素和替考拉宁相关的分子结构 这为新的发展提供了一个具有挑战性的机会 独特的二芳基醚的构筑方法 敏感的附着氨基酸和多肽功能。合成的 研究这些化合物及其结构类似物的方法有 由于……的出现而变得越来越重要 过去对万古霉素耐药的感染性细菌菌株 十年。 手性辅助导向的碳亲核试剂的不对称加成反应 给电子取代芳烃金属络合物提供了一种独特的 一种潜在有效的方法，用于转换现成的 芳香族分子本身转化为光学纯的环己烯酮 合成医学上重要的化合物的重要构件 萜类和类固醇。此应用程序建议继续使用 探索P.I.S实验室开发的一种方法，基于 关于芳烃-锰和芳烃-铬络合物的化学， 这导致了前所未有的和意想不到的 非对映选择性。

The broad, long-term aims of this proposal are to develop applications of arene-metal pi complexes to the total synthesis of challenging molecular arrays that are components of important natural product molecules, and to develop new methodology for asymmetric synthesis based on chiral auxiliary-directed nucleophile additions to arene-metal complexes. Investigations will be continued that are directed toward applications of arene-manganese tricarbonyl and arene(cyclopentadienyl) ruthenium cations in the synthesis of ristocetin A, a complex glycopeptide that is related to vancomycin and teicoplanin, the molecular structures of which present a challenging opportunity for the development of new and unique methodology for the construction of diaryl ethers having sensitive attached amino acid and peptide functionality. Synthetic approaches to these compounds, and their structural analogs, have become increasingly important as a result of the emergence of vancomycin-resistant strains of infectious bacteria during the past decade. Chiral auxiliary-directed asymmetric additions of carbon nucleophiles to donor-substituted arene-metal complexes provides a unique and potentially efficient method for the conversion of readily available aromatic molecules into optically pure cyclohexenones, themselves important building blocks for the synthesis of medicinally important terpenoids and steroids. This application proposes a continuing exploration of an approach developed in the P.I.'s laboratory, based on the chemistry of arene-manganese and arene-chromium complexes, which has resulted in unprecedented and unexpected diastereoselectivities.