Vinylogous Amide Photochemistry in Organic Synthesis

描述（由申请人提供）：本提案旨在开发复杂多环体系立体选择性构建的新方法，并将该方法应用于具有生物学意义的结构的合成。我们在此描述了我们为合成过氢吲哚而开发的分子内葡萄酰胺光环加成/反曼尼希/曼尼希序列的扩展，通过分子内葡萄酰胺亚胺的光环加成合成桥接三环胺酮。本文将通过合成三种不同的含氮杂环[3.2.1]辛烷值的天然化合物来考察光环加成反应的不对称变体的发展：1)足部碱1，来自亚里斯木属，具有抗人乳腺癌细胞的活性；2)securinine 2，是一种特异性GABA受体拮抗剂；3)saraina3，一种由海绵Reniera sarai产生的具有抗肿瘤、抗菌和杀虫活性的海洋生物碱。

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.