Cu(I)催化苯甲醛和2-氨基吡啶反应的理论研究

Theoretical study on the reaction of benzaldehyde and 2-aminopyridine with Cu(I)-catalyzed

摘要:

本文采用密度泛函理论研究了苯甲醛和2-氨基吡啶在Cu(I)催化下反应生成N-(吡啶-2-基)苯甲酰胺的微观机理. 在PW91/DNP基组水平上优化了反应物、过渡态、中间体及产物的几何构型, 通过振动分析确认了过渡态的结构. 报道了四条可能的反应路径. 结果表明: 两种Cu(I)催化剂中, CuI的催化效果优于Cu2O. 通过四条路径速控步骤活化能比较得出路径Re→IMA1→TSA1→IMA2→TSA2→IMA3→TSA3→IMA4→IM6→TS4→P具有相对较低的活化能, 是反应的主要通道, 其速控步骤IM6→TS4→P的活化能是260.12 kJ/mol, 反应热为93.01 kJ/mol. 理论预测的主要产物与实验结果吻合.

Abstract:

The reaction mechanism of benzaldehyde and 2-aminopyridine Cu(I)-catalyzed to form N-(pyridin-2-yl)benzamide were studied by density functional theory. The geometries of the reactants, transition states, intermediates and products were optimized at the PW91/DNP level. Vibration analysis was carried out to confirm the transition state structure. Four possible reaction pathways were investigated in this study. The result indicates that the CuI is better suitable catalyst for producing N-(pyridin-2-yl)benzamide through CuI and Cu2O of Cu(I)-catalyzed. By comparison, the reaction Re→IMA1→TSA1→IMA2→TSA2→IMA3→TSA3→IMA4→IM6→TS4→P is the main pathway, the activation energy of which is the lowest. IM6→TS4→P is the rate-limiting step, with the activation energy being 260.12 kJ/mol and the reaction heat being 93.01 kJ/mol. The dominant product predicted theoretically is in agreement with the experiment results.