PERICYCLIC REACTIONS FOR ORGANIC SYNTHESIS

有机合成的周环反应

• 批准号: 6881195
• 负责人: RICK L DANHEISER
• 金额: $ 29.01万
• 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 2006-03-31
• 项目状态: 已结题
• 来源: https://reporter.nih.gov/project-details/6881195
• 关键词: Diels Alder reaction; alkynes; antiviral agents; chemical addition; chemical synthesis; cyclic compound; cyclic ketone; cyclization; cycloalkene; diterpenes; drug design /synthesis /production; enzyme inhibitors; heterocyclic compounds; invertebrate hormone; ketene; protein tyrosine kinase

DESCRIPTION: (provided by applicant) 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 sixmembered aromatic, heteroaromatic, and dihydroaromatic systems. Intramolecular (4+2) cycloaddition reactions of conjugated enynes will be investigated and employed in new routes to highly condensed polycyclic systems. Heterocyclic variants of this process will be developed leading to five- and six-membered nitrogen and oxygen heterocycles. The application of this chemistry to the synthesis of furanophenalenone diterpenes, pentacyclic 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 development of new methods for the synthesis of conjugated, unsaturated ketenes and their use in new annulation strategies for the synthesis of five-, six-, and seven-membered carbocyclic and heterocyclic compounds. Part III 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 nematode hatching stimulus agent glycinoeclepin A.

说明：（由申请人提供）本提案侧重于申请 周环反应的新方法，用于合成几个 碳环和杂环有机化合物的重要类别。 第一部分介绍了新战略的发展，为综合五个- 和六元芳族、杂芳族和二氢芳族体系。 共轭烯炔的分子内（4+2）环加成反应将是 研究并应用于高浓缩多环体系的新途径。 该方法的杂环变体将被开发，导致五个-和 六元氮和氧杂环。适用本 五环呋喃并菲腊酮二萜合成化学 具有蛋白酪氨酸激酶抑制作用的聚酮海洋天然产物 活性，以及合成抗病毒剂假鹰爪碱B （马匹辛酮）也将进行检查。 建议的第二部分介绍了制定新的方法， 共轭不饱和烯酮合成及其在新的成环反应中的应用 五元、六元和七元碳环的合成策略， 杂环化合物。 该提案的第三部分描述了串联炔丙基 不对称反电子需求分子内乙烯基丙二烯 Diels-Alder策略中的一种异常简洁的方法 线虫孵化刺激剂甘氨菌素A的合成。