Photoinduced proton transfer reactions of diazoalkanes

重氮烷的光诱导质子转移反应

• 批准号: 449797123
• 负责人: Professor Dr. Rene M. Koenigs
• 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: 2020
• 资助国家: 德国
• 起止时间: 2019-12-31 至 2023-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/449797123?language=en
• 关键词: Photoinduced; proton; transfer; reactions; diazoalkanes

Photoinduced proton transfer reactions are an important concept in the development of photoacids and photobases, which find common application in materials chemistry and chemical biology. Applications of photoinduced proton transfer reactions in organic synthesis are even today underdeveloped and mainly limited to the use of high-energy UV light. The understanding and identification of suitable conditions to conduct photoinduced proton transfer reactions under visible light irradiation at ambient conditions is therefore an important task in the development of sustainable synthesis methodology and to understand this conceptual approach towards organic synthesis.In this research project, we plan a systematic study on photoinduced proton transfer reactions of diazoalkanes with different X-H acidic compounds with the aim of understanding the fundamentals and the further exploration of this novel reaction concept. To achieve this goal, we will study the interaction between X-H acidic compounds and diazoalkanes to identify requirements of both reaction partners for efficient proton transfer reactions. These studies comprise detailed mechanistic experiments and basic DFT calculation for the calculation of pKA values. Further applications will involve the exploration of different X-H acidic compounds, such as thiophenols, amides, hydroxamic acids or oximes to expand this concept in a more general way. In a last part, the diazoalkane reaction partner will be studied comprehensively featuring acceptor-only, donor-only or other double substituted diazoalkanes to fully explore this concept from the end of the diazoalkane reaction partner.

光诱导质子转移反应是光酸和光碱发展中的一个重要概念，在材料化学和化学生物学中有着广泛的应用。即使在今天，光诱导质子转移反应在有机合成中的应用仍然不发达，并且主要限于高能紫外光的使用。因此，了解和确定在环境条件下可见光照射下进行光诱导质子转移反应的合适条件是开发可持续合成方法和理解这种有机合成概念方法的一项重要任务。在这个研究项目中，我们计划系统研究重氮烷与不同X-H酸性化合物的光诱导质子转移反应，旨在了解基本原理并进一步探索这一新的反应概念。为了实现这一目标，我们将研究 X-H 酸性化合物和重氮烷之间的相互作用，以确定两种反应伙伴对有效质子转移反应的要求。这些研究包括详细的机理实验和用于计算 pKA 值的基本 DFT 计算。进一步的应用将涉及探索不同的 X-H 酸性化合物，例如苯硫酚、酰胺、异羟肟酸或肟，以更普遍的方式扩展这一概念。最后一部分将对重氮烷反应伙伴进行全面研究，包括仅受体、仅供体或其他双取代重氮烷，从重氮烷反应伙伴的末端充分探索这一概念。