Aromatization-Based Methodology in the Synthesis of Designed and Naturally Occurring Pi Systems with Unusual Structures and Useful Properties

基于芳构化的方法合成具有不寻常结构和有用特性的设计和自然发生的 Pi 系统

• 批准号: 138554-2013
• 负责人: Bodwell, Graham
• 金额: $ 3.93万
• 依托单位: Memorial University of Newfoundland
• 依托单位国家: 加拿大
• 项目类别: Discovery Grants Program - Individual
• 财政年份: 2017
• 资助国家: 加拿大
• 起止时间: 2017-01-01 至 2018-12-31
• 项目状态: 已结题
• 来源: https://www.nserc-crsng.gc.ca/ase-oro/Details-Detailles_eng.asp?id=632795
• 关键词: Aromatization; Based; Methodology; Synthesis; Designed

The overarching objective of the proposed research is to exploit methodology in the field of organic synthesis that has been developed in my group to design and synthesize polycyclic aromatic and heteroaromatic compounds with unusual structures and/or potentially useful properties. The synthesis of molecules with unusual structures is challenging because such systems are necessarily high in energy. The methodology used by my group to generate energetically unfavourable (and therefore very interesting and potentially useful) molecules owes its success to reactions that result in the formation of one or more "aromatic" rings. These energetically advantageous processes offset the disadvantages of forming distorted structures. Bending and battering molecules into shapes that deviate from ideal parameters in a systematic fashion provides an opportunity to learn about the relationships between changes in structure and changes in properties. This knowledge may then be used to design molecules with tailored properties, which may prove to be useful for a variety of applications, include sensors and optoelectronic devices. The research described in this proposal hinges upon a "valence isomerization / dehydrogenation" reaction, which affords severely bent polycyclic aromatic systems, and a multicomponent reaction based on the "inverse electron demand Diels-Alder" reaction, which affords complex heteroaromatic compounds in one fell swoop from three separate starting materials. Prominent polycyclic aromatic targets are molecular helixes, half-belts, belts and Möbius strips. Not only are these systems of considerable fundamental interest, but (in the case of the belts) may also serve as seeds for the controlled growth of "single chirality" single-walled carbon nanotubes. This would provide a solution to an unsolved problem in the field of materials science. The multicomponent reaction will be used to gain rapid access to a variety of polycyclic aromatic and heteroaromatic systems, including biologically active natural products and their analogues, helical molecules and inherently chiral fluorescent compounds.

本研究的总体目标是利用我的团队在有机合成领域开发的方法，设计和合成具有特殊结构和/或潜在有用性质的多环芳香族和杂芳香族化合物。具有特殊结构的分子的合成具有挑战性，因为这样的系统必须具有高能量。我的团队所使用的生成能量不利（因此非常有趣和潜在有用）分子的方法，其成功归功于导致形成一个或多个“芳香”环的反应。这些能量上有利的过程抵消了形成扭曲结构的缺点。以系统的方式将分子弯曲和撞击成偏离理想参数的形状，为了解结构变化和性质变化之间的关系提供了机会。这些知识可以用来设计具有定制特性的分子，这可能被证明对各种应用有用，包括传感器和光电器件。本提案中描述的研究取决于“价异构化/脱氢”反应，该反应提供严重弯曲的多环芳烃体系，以及基于“逆电子需求Diels-Alder”反应的多组分反应，该反应从三种不同的起始材料中一次性提供复杂的杂芳烃化合物。突出的多环芳烃靶标是分子螺旋、半带、带和Möbius条带。这些系统不仅具有重要的基础意义，而且（在带的情况下）也可以作为“单手性”单壁碳纳米管受控生长的种子。这将为材料科学领域的一个尚未解决的问题提供一个解决方案。多组分反应将用于快速获得各种多环芳烃和杂芳烃体系，包括生物活性天然产物及其类似物，螺旋分子和固有手性荧光化合物。