SYNTHESIS OF CYCLOPENTANOIDS BY PHOTOCYCLOADDITONS

光环负载法合成环戊烷类化合物

• 批准号: 3295668
• 负责人: MICHAEL T. CRIMMINS
• 金额: $ 14.78万
• 依托单位: UNIV OF NORTH CAROLINA CHAPEL HILL
• 依托单位国家: 美国
• 财政年份: 1991
• 资助国家: 美国
• 起止时间: 1991-07-01 至 1994-06-30
• 项目状态: 已结题
• 来源: https://reporter.nih.gov/project-details/3295668
• 关键词: chemical addition; chemical bond; chemical synthesis; cyclic ketone; cyclization; cycloalkene; cyclopentane; diene; inhibitor /antagonist; lactones; metal complex; photochemistry; platelet activating factor; stereochemistry; terpenes

Studies are proposed to execute a total synthesis of the potent platelet activating factor antagonists, the ginkgolides, including ginkgolide A, B, bilobalide, crinipellin A, paniculatine and lubimol. This will involve the investigation of diastereoselectivity in the photocycloadditions of enones containing two stereogenic centers on the tethering chain. A novel cyclobutyl carbinyl radical fragmentation-ring expansion sequence will also be investigated as a method for the synthesis of spirocarbocyclic ring systems. Intramolecular photocycloadditions on systems with removable tethers will be investigated as a means for controlling the regiochemical and stereochemical results of intermolecular photocycloadditions. The conjugate addition cyclization of zinc-copper homoenolates will be extended to larger rings and more functionally complex systems. Finally, a project directed toward the development of an auxiliary directed asymmetric [2+2] photocycloaddition on 2-carboalkoxycyclopent-2-en-l-ones will be initiated.

提出了研究以执行有效的完全合成 血小板激活因子拮抗剂，银杏，包括 Ginkgolide A，B，Biolobalide，Crinipellin A，Paniculatine和Lubimol。 这将涉及对非对映选择性的研究 eNONES的光载体，包含两个立体中心 拴系链。 一种新型的环丁基碳纤维基片段碎片环 还将研究扩展序列作为一种方法 螺旋可环形环系统的合成。 具有可移动的系统上分子内光载体 将研究TETHERS作为控制区域化学的手段 以及分子间光载体的立体化学结果。 锌 - 碳酸锌均烯醇的共轭加成环化 将扩展到较大的环和功能更复杂的系统。 最后，一个针对发展的项目 辅助定向不对称[2+2]光循环载体 将启动2-碳氧基2-EN-L-酮。