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过程中的一个重要概念，在材料化学和化学生物学中有着广泛的应用。光诱导质子转移反应在有机合成中的应用即使在今天也不发达，并且主要限于使用高能UV光。因此，理解和确定在环境条件下在可见光照射下进行光诱导质子转移反应的合适条件是发展可持续合成方法和理解这种有机合成的概念方法的重要任务。我们计划系统地研究不同X-重氮烷的光诱导质子转移反应，H酸性化合物，旨在了解基本原理和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烃之间的相互作用，以确定有效的质子转移反应的两个反应伙伴的要求。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，如硫酚，酰胺，异羟肟酸或肟，以更普遍的方式扩展这一概念。最后，对重氮烷反应伴侣进行了全面的研究，从重氮烷反应伴侣的末端对这一概念进行了全面的探讨，包括仅含受体、仅含给体或其它双取代重氮烷。