ORGANOMANGANESE COMPLEXES IN ORGANIC SYNTHESIS

有机合成中的有机锰络合物

• 批准号: 3291595
• 负责人: ANTHONY J PEARSON
• 金额: $ 10.11万
• 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 1989-06-30
• 项目状态: 已结题
• 来源: https://reporter.nih.gov/project-details/3291595
• 关键词: carbonyl compound; chemical synthesis; drug design /synthesis /production; drug screening /evaluation; ethers; glycopeptides; manganese; organometallic compounds; quinones; ristocetin

Arene manganese tricarbonyl complexes provide an excellent means of synthesizing diaryl ethers under extremely mild conditions. We have explored the application of this technique for preparing diaryl ethers having amino acid side chains, as a model for ristocetin synthesis, and the coupling reaction proceeds without loss of optical activity of the protected amino acid. It is proposed to set in hand a detailed investigation into the synthesis of haloarene-Mn(CO)3 complexes containing funcitonalized substituents and to study the displacement of halide by a range of substituted phenoxides and other nucleophiles. A number of simple but important natural products, such as isomagnolol, cularines, and neothalibrine, will be synthesized to illustrate the usefulness of this technique. Ultimately, manganese complexes will be made available which can be applied to the construction of the novel triaryldiether and diaryl ether amino acid subunits found in the glycopeptide anitibiotics related to ristocetin. A total synthesis of ristocetin is a formidable undertaking, but as a long term objective is extremely important, since these compounds are potentially valuable broad spectrum antibiotics which are useful in the treatment of staphylococcal infections when other antibiotics are ineffective. New methods for carbon-carbon bond formation using triene-Mn(CO)3 and dienyl-Mn(CO)3 complexes will be investigated, with a view to their ultimate application as organic synthesis intermediates. Particular attention will be paid to the use of manganese carbonyl to effect the formation of polyquinane derivatives.

芳烃三羰基锰络合物提供了一种极好的方法， 在极其温和的条件下合成二芳基醚。 我们有 探索了该技术在制备二芳基醚中的应用 具有氨基酸侧链，作为Ristoclavine合成的模型， 偶联反应进行而不损失所述化合物的光学活性。 被保护的氨基酸。 建议制定详细的 卤代芳烃-Mn（CO）_3配合物的合成研究 官能化取代基，并研究了卤化物的置换， 一系列取代的酚盐和其他亲核试剂。 一些简单的 但重要的天然产物，如异Magnolol，cularines， 新他利宾，将被合成，以说明这一有用性 法 最终，将提供锰络合物， 可应用于新型三芳基二醚和二芳基二醚的构建， 在糖肽抗生素中发现的醚氨基酸亚基与 Ristoclavia。 全面综合东正教是一项艰巨的任务， 但作为一个长期目标是非常重要的，因为这些化合物 是潜在有价值的广谱抗生素， 治疗葡萄球菌感染时，其他抗生素 无效。 使用三烯-Mn（CO）3形成碳-碳键的新方法和 二烯基锰（CO）3配合物将进行研究，以期其 最终作为有机合成中间体的应用。 特别 将注意使用羰基锰来实现 聚喹烷衍生物的形成。