Vinylogous Amide Photochemistry in Organic Synthesis

有机合成中的乙烯酰胺光化学

• 批准号: 6888036
• 负责人: JEFFREY D WINKLER
• 金额: $ 20.99万
• 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/6888036
• 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）：该提案旨在开发用于立体选择性构建复杂多环系统的新方法，并将该方法应用于合成具有生物学意义的结构。我们在此描述了我们为合成全氢吲哚而开发的分子内插烯酰胺光环加成/逆曼尼希/曼尼希序列扩展到通过插烯酰亚胺的分子内光环加成合成桥联三环氨基酮。将在合成三种不同的天然存在的含有氮杂双环[3.2.1]辛烷部分的化合物的背景下，检查光环加成反应的不对称变体的发展：1) pedunulousine 1，来自亚里士多德属，它表现出针对人乳腺癌细胞，2) securinine 2，一种特异性 GABA 受体拮抗剂，3) sarain A 3，一种海洋生物碱，具有海绵 Reniera sarai 产生的抗肿瘤、抗菌和杀虫活性。

项目成果

A one-step synthesis of 2,3-dihydro-4H-pyran-4-ones from 3-ethoxy alpha,beta-unsaturated lactones.

从 3-乙氧基 α,β-不饱和内酯一步合成 2,3-二氢-4H-吡喃-4-酮。

• DOI: 10.1021/ol050702z
• 发表时间: 2005
• 期刊: Organic letters
• 影响因子: 5.2
• 作者: Winkler,JeffreyD;Oh,Kyungsoo
• 通讯作者: Oh,Kyungsoo