CAJ | 학술논문

采用密度泛函理论的B3LYP泛函对铜催化的炔基酮与重氮酯的[4+1]环加成反应进行了理论研究.根据计算结果,我们确定了两条反应路线,并对其中各驻点的结构进行了全优化,对重要的过渡态进行了IRC扫描以确认其合理性.通过比较两条反应路线中各过渡态的活化能,我们得到了反应的优势路线,确定了反应的机理.采用极化连续介质模型(PCM),考虑了溶剂ClCH_2CH_2Cl对反应中各物种能量的影响.计算结果表明,重氮酯先去氮生成金属卡宾,然后金属卡宾再参与后续的反应,通过[4+1]环加成反应生成多取代呋喃.
채용밀도범함이론적B3LYP범함대동최화적결기동여중담지적[4+1]배가성반응진행료이론연구.근거계산결과,아문학정료량조반응로선,병대기중각주점적결구진행료전우화,대중요적과도태진행료IRC소묘이학인기합이성.통과비교량조반응로선중각과도태적활화능,아문득도료반응적우세로선,학정료반응적궤리.채용겁화련속개질모형(PCM),고필료용제ClCH_2CH_2Cl대반응중각물충능량적영향.계산결과표명,중담지선거담생성금속잡빈,연후금속잡빈재삼여후속적반응,통과[4+1]배가성반응생성다취대부남.
The reaction mechanism of the Cu(I)-catalyzed [4+1] cycloadditions between α,β-acetylenic ketones and diazoacetates is studied using the density functional theory (DFT) with the B3LYP functional. The results indicate that there are two possible reaction paths, and all the geoemtries of intermediates and transition states are optimized completely. The rationality of the geometries of some key transition states are affirmed using the IRC scan. The reaction mechanism is predicted based on the calculated dominant path. In addition, the PCM model is used to consider the solvent effect in C1CH_2CH_2C1. The calculated results indicate that the diazo compounds release the N_2 and lead to the metal carbene; then the subsequent reactions are triggered by the metal carbene, and the furan derivatives are producted by the [4 + 1] Cycloadditions.