本文選題：鎳催化 + 偶聯(lián)反應(yīng)�。� 參考：《上海應(yīng)用技術(shù)大學(xué)》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(lián)反應(yīng),在較溫和的條件下即可實(shí)現(xiàn)烯烴類化合物的高產(chǎn)率制備,該方法具有底物適應(yīng)性好,化學(xué)選擇性優(yōu)異等特點(diǎn)。通過(guò)對(duì)鹵代芳香化合物與烯基溴類底物的反應(yīng)進(jìn)行考察,發(fā)現(xiàn)該方法表現(xiàn)出了較好的空間選擇性,從溴代烯烴的順?lè)椿旌衔锍霭l(fā),主要得到反式烯烴的優(yōu)勢(shì)構(gòu)象化合物;同時(shí),該方法也表現(xiàn)出了良好的官能團(tuán)耐受性,對(duì)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(lián)實(shí)現(xiàn)烯烴類化合物的制備。對(duì)于反應(yīng)機(jī)理也進(jìn)行了探討,通過(guò)深入開(kāi)展自由基捕獲、錳粉代替鋅粉作為還原劑等實(shí)驗(yàn)以及DFT(密度泛函理論)計(jì)算,提出了較為合理的反應(yīng)機(jī)理推斷。Ar-NiⅡ(L)-Ⅰ中間體的成功合成以及參與的實(shí)驗(yàn),進(jìn)一步驗(yàn)證了可能的反應(yīng)機(jī)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(hào)：1993800