PERICYCLIC REACTIONS FOR ORGANIC SYNTHESIS

有机合成的周环反应

• 批准号: 6179441
• 负责人: RICK L DANHEISER
• 金额: $ 23.26万
• 依托单位: MASSACHUSETTS INSTITUTE OF TECHNOLOGY
• 依托单位国家: 美国
• 财政年份: 1980
• 资助国家: 美国
• 起止时间: 1980-07-01 至 2002-03-31
• 项目状态: 已结题
• 来源: https://reporter.nih.gov/project-details/6179441
• 关键词: Diels Alder reaction; alkynes; antiviral agents; chemical addition; chemical synthesis; cyclic compound; cyclization; cycloalkene; drug design /synthesis /production; enzyme inhibitors; heterocyclic compounds; invertebrate hormone; ketene; protein tyrosine kinase

This proposal focuses on the application of pericyclic reactions in new methodology for the synthesis of several important classes of carbocyclic and heterocyclic organic compounds. Part I describes the development of new strategies for the synthesis of five- and six- membered aromatic, heteroaromatic, and dihydroaromatic systems. Intramolecular [4+2] cycloaddition reactions of conjugated enzymes will be investigated and employed in new routes to highly condensed polycyclic systems. Heterocyclic variants of this process will be developed leading to substituted pyridines, dihydroisobenzofurans, and isoindoles. The application of this chemistry to the synthesis of pentacylic polyketide marine natural products with protein tyrosine kinase inhibitory activity and to the synthesis of the antiviral agent nothapodytine B (mappicine ketone) will also be examined. Part II of the proposal describes the application of a tandem propargylic rearrangement-asymmetric inverse electron-demand intramolecular vinylallene Diels-Alder strategy in an exceptionally concise approach to the total synthesis of the nematod hatching stimulus agent glycinoeclepin A. Part III of the proposal describes the development of a new method for the synthesis of (trialkylsilyl) vinyl- and alkynylketens and application of these compounds in new cycloadditions processes leading to five- and six-membered carbocyclic and heterocyclic compounds.

本建议着重于周环反应在合成中的应用， 新的方法学的几个重要类别的合成 碳环和杂环有机化合物。 第一部分介绍了新的战略发展的综合 五元和六元芳族、杂芳族和 二氢芳族体系。 分子内[4+2]环加成 结合酶的反应将被研究和应用于 高浓缩多环系统的新途径。 杂环 该过程的变体将被开发，以取代 吡啶、二氢异苯并呋喃和异吲哚。 的应用 本化学合成的五环聚酮海洋 具有蛋白酪氨酸激酶抑制活性的天然产物， 抗病毒药物假鹰爪碱B（mappicine）的合成 酮）也将进行检查。 提案的第二部分描述了串联的应用 炔丙基排斥-不对称反电子需求 分子内乙烯基丙二烯Diels-Alder策略 一种全综合的简明方法 刺激剂甘氨菌素A。 提案的第三部分介绍了一种新方法的发展 用于合成（三烷基甲硅烷基）乙烯基和炔基烯酮， 这些化合物在新的环加成方法中的应用 导致五元和六元碳环和杂环 化合物.