Vinylogous Amide Photochemistry in Organic Synthesis

有机合成中的乙烯酰胺光化学

• 批准号: 6734223
• 负责人: JEFFREY D WINKLER
• 金额: $ 21.16万
• 依托单位: UNIVERSITY OF PENNSYLVANIA
• 依托单位国家: 美国
• 财政年份: 2003
• 资助国家: 美国
• 起止时间: 2003-05-01 至 2006-04-30
• 项目状态: 已结题
• 来源: https://reporter.nih.gov/project-details/6734223
• 关键词: antineoplastics; chemical addition; chemical synthesis; cyclic ketone; cyclization; imides; indoles; marine toxins; neurotransmitter antagonist; photochemistry; stereochemistry

DESCRIPTION (provided by applicant): This proposal is directed towards the development of new methodology for the stereoselective construction of complex polycyclic ring systems and the application of this methodology to the synthesis of structures of biological significance. We describe herein the extension of the intramolecular vinylogous amide photocycloaddition/retro-Mannich/Mannich sequence that we have developed for the synthesis of perhydroindoles to the synthesis of bridged tricyclic aminoketones via intramolecular photocycloaddition of vinylogous imides. The development of the asymmetric variant of the photocycloaddition reaction will be examined, in the context of syntheses of three different naturally occurring compounds containing the azabicyclo[ 3.2.1]octane moiety: 1) peduncularine 1, from the genus Aristotelia, which displays activity against human breast cancer cells, 2) securinine 2, which is a specific GABA receptor antagonist, and 3) sarain A 3, a marine alkaloid with antitumor, antibacterial, and insecticidal activity produced by the sponge Reniera sarai.

描述（由申请人提供）：该提案是针对复杂多环形系统的立体选择性结构的新方法的开发，并将这种方法应用于生物学意义的结构的综合。我们在此描述了分子内乙烯基乙烯基酰胺光载体的扩展/retro-mannich/mannich序列，我们开发了用于合成旁氢吲哚与桥接三环氨基酮通过静脉内光子载量的静脉三环氨基酮合成的延伸。将在三种不同的自然存在的化合物的合成中，含有azabicyclo [3.2.1]辛烷基因部分：1）peduncarine 1，从阿里斯托氏素（属）属于人类的乳腺癌细胞的活性，3个是Securin and Seeparin，是Securin and Seeparin，是Securin and Asearine 2）海绵Reniera Sarai产生的抗肿瘤，抗菌和杀虫活性的海洋生物碱。