基于多元醇氢转移反应构建含氮杂环的研究

Polyols are widely distributed in nature, the project on effective converting these cost-effective polyol resources into valuable products that could meet the needs of human-being would be of important significance. Meanwhile, it would be also a pathway that meets the points of sustainable development. On the basis of these ideas, we would like to set up a library of phosphine-nitrogen-phosphine pincer ruthenium complexes, and employ these complexes to catalyze the hydrogen-transfer reactions of polyols to construct valuable nitrogen-containing heterocycles; To understand the basic relationship of catalyst structure and catalytic activity,and its influence on the reaction selectivity,and to develop a number of higly efficient, selective ruthenium catalysts.Based on these works, we will get insight into the manners of ligands and metal's actions on dehydrogenation and hydrogen-transfer processes, the modes of cleavage and re-formation of chemical bonds during the construction of N-heterocycles, and set up or enrich the theory of N-heterocycle construction via hydrogen-transfer reactions of polyols.By exploring the scope of the catalytic reactions, the ultimate goal of this project is to develop a number of successful examples on efficient converting polyols into valuable nitrogen-containing heterocycles. The implementation of this project will provide some important methods，theoretical basis and technical support for highly efficient and valuable utilization of polyols, as well for sustainable production of a number of important organic chemicals，enrich the connotation of hydrogen-transfer reactions，and promote the new development of sustainable chemistry.

多元醇广泛地存在于自然界中，如何有效地利用这些廉价资源，将其转化为高值化的产品以满足人类的需求将是一项具有重要意义的研究课题，也是一条符合可持续发展要求的道路。基于以上理念，我们拟构建一个新型的膦-氮-膦钌螯合物库，将其应用于催化多元醇的氢转移反应构建具有重要应用价值的含氮杂环产物；明确催化剂结构和催化活性之间的基本关系以及对反应选择性的影响情况，发展出若干高效、高选择性的催化剂；在此基础上，进一步探索配体和金属对醇脱氢和氢转移的作用方式、氮杂环形成过程中键的选择性断裂与可控性组合的模式，发展或完善多元醇氢转移反应构建氮杂环的理论体系；拓展催化反应的应用范围，最终发展出若干多元醇高效构建氮杂环的成功案例。本项目的开展将为多元醇资源的高效、高值化利用及若干重要有机化学品的可持续化生产提供一些重要方法、理论依据和技术支撑；并将丰富氢转移反应的内涵、促进可持续化学的新发展。

醇是一类价廉易得的可再生资源，通常由农作物通过发酵、木质素等经化学转化而得到。氮杂环存在于各种功能化产物中，被广泛地用于制备各种药物、功能材料、配体、化学传感器、颜料燃料等。因此，发展有效的方法，将醇资源高效、选择性转化为氮杂环产物是一些具有重要意义的研究课题。本项目研究通过发展高效的催化体系，利用氢转移策略，发展了一系列由醇转化为芳杂环的新合成方法；经催化剂活性评估，我们明确了若干催化体系中催化剂的构效关系；经机理探索研究，我们提出相应的反应机理，形成了醇转化为氮杂环的初步理论体系。在此基础上，我将氢转移偶联中的脱氢与氢转移应用于富氢体系环胺的催化转化，为环胺的高效、选择性转化奠定了初步基础。本项目的开展为醇资源的高效、高值化转化利用及若干功能化氮杂环的高效、选择性合成提供了重要方法、理论依据和技术支撑，丰富了绿色合成化学的内涵，并为氢转移偶联理念的进一步应用开辟了新道路。