ARENE ACTIVATION BY TRANSITION METALS

芳锰三羰基和芳烃(环戊二烯基)Ru 络合物已被证明是有用的前体。 两个芳香环均带有二芳基醚的结构 受保护的氨基酸侧链。建议的主旨是 研究是这一新方法论向 与糖肽相关的七肽芳醚的合成 可能有用的抗生素万古霉素和瑞斯托菌素A 对抗革兰氏阳性细菌。一系列简化的多环化合物 将合成多肽/芳基醚，并将其与简单 Ac-D-Ala-D-Ala、Ac2-L-Lys-D-Ala-D-Ala等 代表细菌细胞壁的前体，将被研究。信息 与重大约束的最低结构要求有关 因此，将获得交互。对更广泛的问题进行平行研究 将开展芳烃-铁和芳烃-Ru络合物的应用 由于这些综合体承诺提供一种建造 某些芳基醚不能使用有机锰 化学反应。两个重要的化学反应将在所有 这些研究包括：(1)在卤代芳烃金属上加成酚氧化物 络合物，然后(2)加成手性甘氨酸烯醇酸等效物 到第一次反应产生的芳基醚金属体系。 芳烃-Ru络合物在二叔丁基酪氨酸合成中的应用 衍生物和抗生素布瓦丁，K-13和494-III将 也要接受检查。

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.