Synthesis of helicenes and related compounds

螺烯及相关化合物的合成

• 批准号: 321658745
• 负责人: Professor Dr. Joachim Podlech
• 金额: --
• 依托单位: Institut für Organische Chemie (IOC)
• 依托单位国家: 德国
• 项目类别: Research Grants
• 财政年份: 2016
• 资助国家: 德国
• 起止时间: 2015-12-31 至 2019-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/321658745?language=en
• 关键词: Synthesis; helicenes; related; compounds

Metal-catalyzed reactions of alpha-functionalized biphenyls with acetylenes and nitriles lead to phenanthrenes and nitriles, respectively. This well-known transformations shall be extended to functionalized acetylenes and nitriles to finally yield perylene quinones, benzo[de]anthracenes and benzoacridines. Starting with suitably substituted and thus chiral biphenyls would lead to enantiomerically pure, axially chiral perylene quinones. In expansion of this strategy, the reaction of oligo-ortho-phenylenes with acetylenes or nitriles would furnish helicenes and aza-helicenes, respectively. With this, the synthesis of substituted helicenes could be achieved. Since oligophenylenes are available in enantiomerically pure form, the enantioselective synthesis of helicenes is possible. Multiple Friedel-Crafts acylation of oligophenylenes with carboxyl chloride functions in the alpha positions would yield new helicene analogues with keto functions in the periphery, which could be further transformed and functionalized. Interesting physical properties can be expected for these compounds

金属催化的α-官能化联苯与乙炔和腈的反应分别导致菲和腈。这一众所周知的转化将被扩展到官能化的乙炔和腈，以最终产生二萘嵌苯醌、苯并[脱]蒽和苯并吖啶。从适当取代的手性联苯开始，将得到对映体纯的轴向手性二萘嵌苯醌。在该策略的扩展中，低聚邻苯与乙炔或腈的反应将分别提供螺烯和氮杂螺烯。由此，可以实现取代螺烯的合成。由于低聚亚苯基可以对映体纯的形式获得，因此螺旋烯的对映选择性合成是可能的。在α位上具有羧基氯官能团的低聚亚苯基的多重Friedel-Crafts酰化将产生在外围具有酮基官能团的新的螺烯类似物，其可以进一步转化和官能化。这些化合物具有有趣的物理性质