【摘要】：過(guò)渡金屬催化烯丙基取代反應(yīng)已經(jīng)成為構(gòu)建C-C鍵、C-N鍵、C-O鍵、C-S鍵以及C-P鍵等多種化學(xué)鍵的有效手段。通常制備烯丙基取代產(chǎn)物及其衍生物都是通過(guò)烯丙基化合物與各種親核試劑的取代反應(yīng)來(lái)獲得。這些經(jīng)典的合成方法一般需要已經(jīng)活化了的烯丙基化合物,例如烯丙基鹵代物、烯丙基酯、烯丙基碳酸酯、磷酸酯以及相關(guān)的衍生物等,這些已活化的烯丙基底物都是從相應(yīng)的烯丙基醇制備得來(lái)。反應(yīng)步驟繁瑣,原子經(jīng)濟(jì)性差。因此,直接催化烯丙基醇的親核取代反應(yīng),更具有研究意義和挑戰(zhàn)性。而以廉價(jià)金屬鐵催化劑與雙齒亞磷酸酯配體絡(luò)合來(lái)催化烯丙基醇的取代反應(yīng)鮮少有報(bào)道。本文在研究過(guò)渡金屬催化烯丙基醇的取代反應(yīng)時(shí),發(fā)現(xiàn)Fe(OTf)2與雙齒亞磷酸酯配體一起作用,能夠很好的催化烯丙基醇取代反應(yīng),并取得中等到優(yōu)秀的收率,在有機(jī)合成方法學(xué)上具有一定的創(chuàng)新性和研究意義。本課題組首先合成了六種雙齒亞磷酸酯配體L1-L6,以采用3,3',5,5'-四叔丁基-2,2'-二羥基聯(lián)苯為原料,“一鍋法”高效合成了該類(lèi)型的配體。接下來(lái)我們又考察了雙齒亞磷酸酯配體在烯丙基醇取代反應(yīng)中的應(yīng)用,以肉桂醇與苯胺的反應(yīng)為模板,考察了不同催化劑、溶劑、配體、溫度、催化劑的用量對(duì)烯丙基取代反應(yīng)的影響,并確定了優(yōu)化后的反應(yīng)條件為:在氮?dú)獗Ｗo(hù)下,5mol%Fe(OTf)2為催化劑,5mol%L4作為配體,甲苯作為溶劑,回流的條件下,反應(yīng)12 h。在優(yōu)化后的條件下,對(duì)芳香胺、脂肪胺、硫酚類(lèi)化合物以及不同烯丙基醇類(lèi)化合物進(jìn)行了拓展,取得了高選擇性和中等至優(yōu)秀的收率。
[Abstract]:The catalytic allyl substitution reaction of the transition metal has become an effective means to construct the C-C bond, the C-N bond, the C-O bond, the C-S bond, and the C-P bond. In general, the preparation of allyl-substituted products and their derivatives is obtained by the substitution reaction of allyl compounds with various nucleophiles. These classical synthesis methods generally require the already activated allyl compounds, such as allyl halides, allyl esters, allyl carbonates, phosphate esters, and related derivatives, and the like, all of which are derived from the corresponding allyl alcohol. The reaction steps are complex and the atomic economy is poor. Therefore, the nucleophilic substitution reaction of the allyl alcohol is directly catalyzed, and the research significance and the challenge are more. And the substitution reaction of the allyl alcohol is catalyzed by the complex of the cheap metal iron catalyst and the double-tooth phosphite ligand. In this paper, when the substitution reaction of the transition metal catalyzed allyl alcohol is studied, it is found that the Fe (OTf)2, together with the didentate phosphite ligand, can be used as a good catalytic allyl alcohol to replace the reaction, and the yield of the medium to the excellent is obtained, and the method has certain innovation and research significance in the organic synthesis method. In this research group, six didentate phosphite ligands L1-L6 were synthesized, and the ligands of this type were synthesized by the "one-pot method" of 3,3 ',5,5'-tetrat-butyl-2,2 '-dihydroxybiphenyl. The application of didentate phosphite ligand in the substitution reaction of allyl alcohol was also investigated. The reaction of cinnamyl alcohol and aniline was used as the template, and the effect of different catalyst, solvent, ligand, temperature and catalyst on the reaction of allyl substitution was investigated. and the optimized reaction conditions are as follows: under the protection of nitrogen,5 mol% of Fe (OTf)2 is used as a catalyst,5 mol% of L4 is used as a ligand, and the toluene is used as a solvent, and the toluene is used as a solvent, and the reaction is carried out for 12 hours under the condition of reflux, The sulfur compounds and the different allyl alcohol compounds are expanded to obtain high selectivity and moderate to excellent yield.
【學(xué)位授予單位】：鄭州大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類(lèi)號(hào)】：O641.4;O621.251

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