可见光促进的过渡金属催化惰性化学键选择性转化研究

Transition metal-catalyzed transformations of inert chemical bonds is one of the most competitive and impacting fields of organic chemistry, showing theoretical importance and great potential for industrial applications. Although significant progress has been achieved in the field, there are still a lot of problems and challenges, especially the limitations of catalytic systems and activation modes. Recently, application of visible-light photoredox catalysis in organic synthetic chemistry has been developed significantly to achieve a series of novel free radical chemistry, although with huge challenges to achieve high selectivity. Concerning the remaining problems and challenges in the field of inert bond activation, this project aims to develop novel activation modes with lower energy barrier of oxidative addition to promote inert bond activation under mild reaction conditions by merging visible-light photoredox catalysis and transition metal catalysis. With using inexpensive, robust and active catalyst systems, a series of important cross-coupling reactions will be realized with high efficiency and selectivity to generate carbon-carbon bonds and carbon heteroatom bond as well as important heterocyclic compounds. Moreover, the asymmetric reactions will also be investigated with rational design of chiral ligands. The atom-, step- and redox-economy will be improved in order to provide practical methods. Finally, we will further study the mechanism to explore cooperative effect between transition metal catalysis and visible light photoredox catalysis, providing guidance and base for its extensive use in organic chemistry and for the ultimate utilization of sunlight in chemical industry.

过渡金属催化的惰性化学键转化是有机化学领域中十分具有竞争力的研究方向，具有重要学术意义和工业应用前景。尽管取得了显著进展，但该领域中还有很多难题，如催化体系和活化模式有较大局限性。近年来，可见光催化在有机合成中广泛运用，实现了一系列新颖的自由基化学，但选择性控制较难。针对这些科学问题，本项目拟结合可见光化学和过渡金属催化，开发新颖的催化体系和活化模式，降低惰性化学键的活化能垒，促进其在温和条件下发生氧化加成和进一步选择性转化。建立廉价易得且高活性的催化体系，实现一系列重要交叉偶联反应，高效高选择性地形成碳碳键和碳杂原子键，发展重要杂环化合物的绿色合成方法，努力实现不对称催化反应，不断提高反应的原子、步骤和氧化还原经济性以及实用性。最后，我们将深入研究机理，探索过渡金属催化和可见光催化之间的协同效应，为其在有机化学领域中的大量运用提供理论指导，为最终实现太阳光在工业中的广泛应用提供坚实基础。

近年来，惰性化学键活化和转化备受关注，在促进资源合理利用和减少环境污染方面具有重要意义和应用前景，但是目前催化体系和活化模式具有较大局限。另一方面，可见光催化在有机合成中广泛运用，实现了一系列新颖的自由基化学，但主要局限于高活性底物，并且选择性控制较难。针对这些科学问题，本项目开发了新颖的可见光催化活化模式，建立了廉价易得且高活性的可见光催化体系，在温和条件下促进了一系列惰性化学键（如碳碳键、碳氟键、碳氮键、碳氧键和碳氢键等）、惰性体系（如芳香体系）和惰性小分子（如二氧化碳）的高效选择性转化，实现了一系列重要交叉偶联和羧基化等碳碳成键反应和环化反应，发展了重要生理活性分子、杂环化合物和羧酸的绿色合成方法，提高了反应的原子、步骤和氧化还原经济性以及实用性，并深入研究了反应机理，为其在有机化学、药物和材料等领域中的运用提供了数据支撑，为最终实现太阳光在工业中的广泛应用提供了坚实基础。在项目支持下，我们在国内外期刊上共发表了32篇论文，申请6项中国发明专利，授权1项；并且培养了1名博士后、2名博士、4名硕士和10余名本科生。