ARENE ACTIVATION BY TRANSITION METALS

过渡金属对芳烃的活化

• 批准号: 2749839
• 负责人: ANTHONY J PEARSON
• 金额: $ 21.31万
• 依托单位: CASE WESTERN RESERVE UNIVERSITY
• 依托单位国家: 美国
• 财政年份: 1986
• 资助国家: 美国
• 起止时间: 1986-07-01 至 2001-06-30
• 项目状态: 已结题
• 来源: https://reporter.nih.gov/project-details/2749839
• 关键词: chemical addition; chemical structure function; chemical synthesis; chromium; cycloalkene; cyclohexanones; drug design /synthesis /production; glycopeptides; manganese; metal complex; ristocetin; ruthenium; stereochemistry; vancomycin

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.

该提案的广泛、长期目标是开发应用程序 芳烃-金属π配合物的全合成具有挑战性的 分子阵列是重要的天然产物的组成部分， 分子，并开发新的方法学不对称合成 基于对芳烃-金属的手性定向亲核加成 配合物 将继续进行针对以下应用的调查： 芳烃三羰基锰和芳烃钌 阳离子在合成瑞斯托康A，一个复杂的糖肽， 与万古霉素和替考拉宁相关， 这为开发新的 和独特的方法来构建二芳基醚， 敏感的连接氨基酸和肽功能。 合成 这些化合物及其结构类似物的方法， 由于出现了 万古霉素耐药菌株的感染性细菌在过去 十年 碳亲核试剂的手性非对称加成反应 给体取代的芳烃-金属配合物提供了一种独特的， 一种潜在的有效方法， 芳香分子转化为光学纯的环己烯酮， 重要的组成部分，用于合成具有医学重要性的 萜类化合物和类固醇。 本申请提出一项持续的 P.I.开发的方法的探索。的实验室， 在芳烃-锰和芳烃-铬络合物的化学上， 导致了前所未有的 非对映选择性