轴不对称支撑的手性N-O酰胺化合物催化亚胺硅氢化反应的过渡态研究

Transition State Investigation on Hydrosilylation of Ketoimines with Trichlorosilane Using Asymmetric-axle-supported Chiral N-O Amides

利用Hartree-Fock(HF)算法和密度泛函理论(DFT)探讨了新型轴手性氮氧酰胺类配体催化亚胺C=N双键不对称硅氢化反应的过渡态.研究发现,H在Si原子上,反应经过渡态TS-2,能垒较低,由此得到产物(-)-N-(1-phenylethyl)aniline的e.e.值与实验结果相吻合.同时,本文还尝试采用合理的简化模型计算反应过渡态,其结果与使用全部分子用于过渡态能量计算的结论一致.

The mechanism was investigated for enantioselective hydrosilylation of CN with HSiCl3 catalyzed by a novel asymmetric-axle-supported chiral ligand with Hartree-Fock （ HF ） and density functional theory （DFT） at the 6-31G（d） basis sets, respectively. Molecules of catalyst, ketoimine and HSiCl3 were included in activation energy computations. The energy barriers can well explain the enantioselective reaction e. e. values recorded in experiments. Also, a simplified transition state（ TS） model was adopted in TS calculations, the barrier sequence recorded by the model had a good agreement with the results via using whole substances [catalyst 3 or epi-3, SiHCl3 and （-）-N-（1-phenylethylidene）aniline] in TS calculations, including the e. e. values.