手性噁唑磷烷—硼烷催化活性的理论研究

Theoretical Studies on Catalytical Activity for the Chiral Oxazapholidine—Borane

采用前人的实验结果,用密度泛函理论B3LYP/6-31G*方法对4种催化还原潜手性酮的手性唑磷—硼烷催化剂进行了量子化学计算.根据优化所得催化剂的几何构型和电子结构,从空间效应和电子效应两方面对催化剂分子进行了分析和讨论,以期从理论上揭示取代基对手性唑磷—硼烷催化活性的影响.计算结果表明,催化活性的高低与唑磷烷环上磷原子连接的取代基大小以及唑磷—硼烷中磷、硼原子上的电荷分布有关,研究结果与实验得出的结论基本一致.

The configurations and electronic structure of four oxazaphospolidine—borane catalysts have been explored at the B3LYP/6-31G~*level.The relationship between structure of substitute oxazaphospolidine—borane and catalytic activity has also analyzed.It is found that the catalytic activity of oxazaphospolidine—borane is concerned by various substituents connecting with phosphorus atom and the charge distributing on phosphorus and boron atoms in oxazaphospolidine—borane catalysts.The computational results are in consistence with experiments.