發(fā)布時間：2018-06-08 01:39

  本文選題：鎳催化 + 偶聯反應�。� 參考：《上海應用技術大學》2017年碩士論文

【摘要】：本文發(fā)展了一種鎳催化鹵代芳烴與鹵代烯烴的還原偶聯反應,在較溫和的條件下即可實現烯烴類化合物的高產率制備,該方法具有底物適應性好,化學選擇性優(yōu)異等特點。通過對鹵代芳香化合物與烯基溴類底物的反應進行考察,發(fā)現該方法表現出了較好的空間選擇性,從溴代烯烴的順反混合物出發(fā),主要得到反式烯烴的優(yōu)勢構象化合物;同時,該方法也表現出了良好的官能團耐受性,對于富(缺)電子鹵代芳烴以及雜環(huán)溴代化合物,均能與(非)共軛烯基溴交叉偶聯實現烯烴類化合物的制備。對于反應機理也進行了探討,通過深入開展自由基捕獲、錳粉代替鋅粉作為還原劑等實驗以及DFT(密度泛函理論)計算,提出了較為合理的反應機理推斷。Ar-NiⅡ(L)-Ⅰ中間體的成功合成以及參與的實驗,進一步驗證了可能的反應機理。
[Abstract]:In this paper, a nickel catalyzed reduction coupling reaction of halogenated aromatics with halogenated olefins has been developed. The high yield of alkenes can be prepared under mild conditions. The method has the advantages of good substrate adaptability and excellent chemical selectivity. The reaction of halogenated aromatic compounds with alkenyl bromine substrates was investigated. It was found that the method showed good spatial selectivity. The dominant conformational compounds of trans-olefin were obtained from cis / trans mixtures of brominated olefin. This method also shows good functional group tolerance. For electron-rich halogenated aromatics and heterocyclic brominated compounds, they can be cross-coupled with (non-conjugated) enyl bromide to achieve the preparation of olefin compounds. The reaction mechanism was also discussed. Experiments such as free radical trapping, manganese powder replacing zinc powder as reducing agent and DFT (density functional theory) calculation were carried out. A reasonable reaction mechanism was proposed. The successful synthesis of the intermediate of Ar-Ni 鈪，

本文編號：1993799