过渡金属催化的生物质基多羟基化合物脱氧脱水反应机理研究

本项目拟运用量子化学理论计算和物理有机化学实验相结合的研究手段，系统研究过渡金属催化的生物质基多羟基化合物的脱氧脱水反应机理，阐明钌、铼、钼金属有机络合物催化邻二醇脱氧脱水反应的机理，获取关键中间体和过渡态的结构能量关系，对比不同催化体系的优势反应路径，揭示整个催化循环的决速步，发现影响化学选择性的决定因素，研究配体和还原剂在钒氧化物催化条件下影响反应速率的内在规律。在此基础上，发展新型高效、高选择性的脱氧脱水反应，实现生物质基多羟基化合物在温和条件下的定向转化，提高转化效率和化学选择性，为生物质催化转化提供新的途径。

Combined studies of theoretical calculations and physical-organic experimental characterizations, in the present proposal we shall systematically investigate the mechanism of the transition metal (such as Re, Ru, Mo and V) catalyzed deoxydehydration reactions of biomass-derived polyols. Effort will be emphasized on clarity of the most feasible mechanism of Re, Ru, and Mo catalyzed deoxydehydration of vicinal diols, generation of the inherent structure-energy relationships of the key intermediates and transition states, and the comparison of the similarity/differences between different catalytic systems. The rate-determining step and the origin of the chemo-selectivity could be then generated. What’s more important, we will carry out systemtic studies on the routine influence of the structures of ligands/reductants on the reaction rates in the vanadium oxide catalyzed deoxydehydration reactions. On the basis of the aformentioned mechanistic studies, we will then focus on the development of more powerful and high selective deoxydehydration reactions, with the aim to achieve high efficient transformations of the biomass-derived polyols under mild conditions, and provide novel strategies for catalytic transformations of biomass.