NOVEL RING ENLARGEMENT AND ANNULATION REACTIONS

新颖的环扩大和成环反应

• 批准号: 2180054
• 负责人: PAUL DOWD
• 金额: $ 13.49万
• 依托单位: UNIVERSITY OF PITTSBURGH AT PITTSBURGH
• 依托单位国家: 美国
• 财政年份: 1988
• 资助国家: 美国
• 起止时间: 1988-04-01 至 1997-07-31
• 项目状态: 已结题
• 来源: https://reporter.nih.gov/project-details/2180054
• 关键词: chemical synthesis; cyclic ketone; cyclization; free radicals; heterocyclic compounds

A novel ring expansion and chain extension reaction has been discovered. The new reaction is completely regiospecific, takes place in excellent yield and appears to be capable of very broad application and extension, particularly in the area of medium- sized rings. Accordingly, it is proposed to extend the method to include heterocyclic compounds with emphasis on the pharmacologically useful benzazepines and dibenzazepines. Application to the synthesis of optically active beta-amino acids will be explored. Vinylogous ring expansion and inter- and intramolecular olefin trapping experiments will be carried out. The latter can yield new, efficient annulation methods. In addition to developing the one-carbon ring expansion, preliminary experimental findings have given positive results for three- and four-carbon ring expansions which open many new opportunities. These coupled with multiple ring expansion of keto diesters and diketo tetraesters provide a wealth of opportunity for elaboration of single and fused medium ring systems. The mechanistic premises underlying the reaction will also be examined.

一种新颖的扩环和扩链反应 发现了。 新反应是完全区域特异性的，需要 产量很高，并且似乎能够非常广泛 应用和推广，特别是在中等领域 大小的戒指。 因此，建议将该方法扩展到 包括杂环化合物，重点是 药理学上有用的苯并氮杂卓和二苯并氮杂卓。 在光学活性β-氨基酸合成中的应用 将被探索。 乙烯基环扩张和相互间 将进行分子内烯烃捕获实验。 后者可以产生新的、有效的环化方法。 在 除了开发一碳环扩张之外，初步 实验结果给出了三个和 四碳环扩张开辟了许多新的机遇。 这些与酮二酯的多环扩张相结合， 二酮四酯提供了大量的阐述机会 单环和稠合中环系统。 机械论 还将检查反应的前提。