ARENE ACTIVATION BY TRANSITION METALS

芳烃锰三羰基和芳烃钌 复合物已被证明是有用的前体， 两个芳环均带有 保护的氨基酸侧链。 建议的主旨 研究是这种新方法的发展， 与糖肽相关的七肽芳醚的合成 抗生素万古霉素和瑞斯托霉素A，这是潜在的有用的 对抗革兰氏阳性菌 一系列简化的多环 肽/芳基醚将被合成，并且它们与简单的 肽，如Ac-D-Ala-D-Ala和Ac 2-L-Lys-D-Ala-D-Ala， 代表细菌细胞壁前体，将进行研究。 信息 关于重大约束力的最低结构要求 因此将获得相互作用。 关于更广泛的 芳烃-铁和芳烃-钌配合物的应用将得到开展 因为这些复合物承诺提供一种构建 使用有机锰不能得到的某些芳基醚 化学. 两个重要的化学反应，以在所有 这些研究是（1）将酚盐加成到卤代芳烃-金属上 络合物，然后（2）加入手性甘氨酸烯醇化物等价物 与由第一反应产生的芳基醚金属体系反应。 芳烃钌配合物在合成双酪氨酸中的应用 衍生物和抗生素bouvardin，K-13和OF 494-III将 也要检查。

Arenemanganese tricarbonyl and arene(cyclopentadienyl)ruthenium complexes have been demonstrated to be useful precursors for the construction of diaryl ethers in which both aromatic rings carry protected amino acid side chains. The major thrust of the proposed research is the development of this new methodology towards the synthesis of heptapeptide arylethers related to the glycopeptide antibiotics vancomycin and ristocetin A, which are potentially useful against gram-positive bacteria. A series of simplified polycyclic peptide/aryl ethers will be synthesised and their binding to simple peptides, such as Ac-D-Ala-D-Ala and Ac2-L-Lys-D-Ala-D-Ala, which represent bacterial cell wall precursors, will be studied. Information relating to the minimum structural requirements for significant binding interaction will be thus obtained. Parallel studies on the broader applications of arene-iron and arene-ruthenium complexes will be carried out, since these complexes promise to offer a means of constructing certain aryl ethers that are not available using the organomanganese chemistry. The two important chemical reactions to be employed in all of these studies are (1) addition of phenoxides to a haloarene-metal complex, followed by (2) addition of chiral glycine enolate equivalents to the aryl ether metal system that results from the first reaction. Application of arene-ruthenium complexes in the synthesis of dityrosine derivatives and the antibiotics bouvardin, K-13, and OF 494-III will also be examined.