CO2与炔烃的催化羧基化反应制备高附加值化学品的理论研究

As one of the most important routes for effectively utilizing CO2 resources, transition-metal catalyzed carboxylation of carbon dioxide with alkynes, which could provide high value-added chemical products, has broad application in the fields of medicine development and organic synthesis. Compared with the experimental studies, theoretical studies on the carboxylation of CO2 with alkynes require to be further explored. In this project, based on the quantum chemistry calculation methods, we will perform systematically studies on the carboxylation of alkynes with carbon dioxide catalyzed by Ni and Cu complexes. Our studies will pay substantial attentions on the following aspects: (a) the mechanism details of the catalytic carboxylation of alkynes with carbon dioxide along various possible pathways, (b) the thermodynamic and dynamical properties of the catalytic reactions, (c) the optimal mechanisms of the carboxylation reactions catalyzed by Ni and Cu complexes, (d) key factors controlling the selective activation of terminal alkynes C≡C bond and C–H bond using different metal catalysts, (e) the influence of the reaction substrate, reducing agent on the selectivity of Ni catalysts, and the influence of the ligand, counterion on the catalytic activity of Cu catalysts. Combining with the existing theoretical literature, we will summarize the potential laws on the catalytic activity and selectivity of different transition-metal catalysts. It is believed that the theoretical results would provide valuable basis and theoretical guidance for rationally designing new efficient and environment-friendly catalysts.

温室气体CO2与炔烃的催化羧基化反应是CO2优化利用、变害为宝的重要途径之一，所得不饱和羧酸及其衍生物在药物开发和有机合成领域有着广泛的应用。同实验研究相比，CO2与炔烃催化羧基化反应的理论研究尚有许多问题需要深入。本项目运用量子化学方法对近年来发展的Ni、Cu催化剂催化CO2与炔烃羧基化反应进行理论研究，探索可能的反应路径，分析反应的热力学和动力学性质，确定最优的反应路径，阐明控制Ni、Cu催化CO2与炔烃羧基化反应的关键因素，揭示端基炔C≡C键和C–H键选择性活化的本质影响。在此基础上研究反应底物、还原剂等因素对Ni催化羧基化反应选择性的影响、配体和抗衡离子对Cu催化剂催化反应活性的影响，总结不同金属催化剂催化活性和反应选择性的内在规律。项目的开展可为新型过渡金属催化剂的合成和筛选提供必要的科学依据，具有重要的理论与现实意义。

温室气体CO2催化转化为高附加值的有机化学品是CO2优化利用、变害为宝的重要途径之一。使用过渡金属络合物催化完成羧基化已成为该领域的研究热点。本课题运用量子化学方法，主要对铼催化CO2与氯甲基环氧乙烷的偶联反应进行了理论研究，我们提出了CO配体协助催化的全新反应机理，在该机理中CO作为配体↔羰基的角色互换确保了反应的顺利进行。另外，研究了其他相关重要的金属有机催化反应，阐明了取代基对催化偶联反应活性和选择性的控制因素，路易斯酸对偶联反应选择性的影响，水对催化异构化反应产物选择性的内在本质。本课题工作对于进一步研究CO2的催化转化奠定了基础，为设计高效新型环境友好的催化剂提供重要的设计思路和理论基础。