金属卟啉催化乙苯的不对称羟基化反应是合成手性1-苯乙醇的一类重要反应。普林斯顿大学的John T. Groves教授等人报道了手性铁卟啉催化的乙苯的不对称羟基化反应，R-1-苯乙醇是主要产物。香港大学的支志明教授等人报道了手性钌卟啉催化的乙苯的不对称羟基化反应，S-1-苯乙醇是主要产物。对于这两类重要的不对称羟基化反应机理和选择性的计算研究，尚未见文献报道。我们拟采用理论与计算化学的方法对手性金属卟啉催化的乙苯的不对称羟基化反应进行系统深入的研究。通过对金属卟啉催化循环能量变化的计算，揭示金属卟啉催化的乙苯的羟基化反应的反应机理。在理解反应机理和确定反应决速步的基础上，建立手性金属卟啉催化剂实现不对称羟基化反应的过渡态模型，阐明催化剂和底物控制立体选择性的基本规律。在解释和总结现有实验结果的基础之上，尝试改良已知的手性金属卟啉催化剂以及拓展不对称羟基化反应的底物范围和提高对映体选择性。

Metalloporphyrin-catalyzed asymmetric hydroxylation of ethylbenzene is an important reaction to synthesize chiral 1-phenylethanol. Prof. Jonh T. Groves and coworkers at Princeton University reported the asymmetric hydroxylation by a chiral iron porphyrin, and R-1-phenylethanol was isolated as the major product. Prof. Chi-Ming Che and coworkers at the University of Hong Kong reported the asymmetric hydroxylation by a chiral iron porphyrin, and R-1-phenylethanol was isolated as the major product. To the best of our knowledge, there is no computational study on the mechanism and selectivity of these two important asymmetric hydroxylation reactions. We are planning to carry out systematic and thorough computational studies on the metalloporphyrin-catalyzed asymmetric hydroxylation of ethylbenzene. Through computations of energy changes on the whole catalytic cycle of metalloporphyrin catalysis, we will unveil the mechanism of metalloporphyrin-catalyzed hydroxylation of ethylbenzene. Based on the understanding of the reaction mechanism and determination of the rate-limiting step, we will establish the transition state model for the asymmetric hydroxylation by chiral metalloporphyrins and reveal the principle that how catalyst and substrate control the stereoselectivity. Based on the explanations of the existing experimental results, we will try to modify the chiral catalysts, and to expand the substrate scope and improve the enantioselectivity of the asymmetric hydroxylations.