NOVEL RING-ENLARGEMENT CHAIN-EXTENSION REACTION

新型扩环扩链反应

• 批准号: 3297050
• 负责人: PAUL DOWD
• 金额: $ 9.44万
• 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 1993-03-31
• 项目状态: 已结题
• 来源: https://reporter.nih.gov/project-details/3297050
• 关键词: aminoacid; benzazepines; chemical chain length; chemical reaction; cyclic compound; drug design /synthesis /production; 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.

合成了一种新的扩环扩链反应。 被发现了。这种新的反应完全是地区性的， 处于极好的产量中，并且似乎能够非常广泛地 应用和推广，特别是在媒体领域- 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 药理上有用的苯扎西平和二苯并氮卓类药物。 光学活性β-氨基酸在合成中的应用 将会被探索。乙烯基环扩张和环间 将进行分子内的烯烃捕集实验。 后者可以产生新的、有效的环扎方法。在……里面 除开发单碳环扩张外，初步 实验结果给出了三个和 四碳环的扩张带来了许多新的机会。 这些都与酮二酯的多环扩张和 Diketo四酯为精加工提供了丰富的机会 单环和熔融中环系统。机械论 我们还将考察这些反应背后的前提。