本文選題：手性膦配體　切入點：偶氮甲堿葉立德　出處：《湖南工業(yè)大學(xué)》2017年碩士論文　論文類型：學(xué)位論文

【摘要】：本論文將設(shè)計合成的氨基酸和環(huán)己二胺衍生的膦酰胺配體與過渡金屬絡(luò)合,形成新的催化體系,并將該催化體系應(yīng)用于不對稱[3+2]環(huán)加成反應(yīng)的研究。(1)以氨基酸和環(huán)己二胺為原料,分別設(shè)計合成了單氨基酸衍生的膦酰胺配體10個,雙氨基酸衍生的膦配體6個,環(huán)己二胺和氨基酸衍生的膦酰胺配體4個。(2)將上述不同骨架的膦酰胺配體用于催化偶氮甲堿葉立德與貧電子烯烴的不對稱[3+2]環(huán)加成反應(yīng)。研究了配體、金屬、溶劑和添加劑對催化劑催化性能的影響。確定了配體1g,1p和1t為最優(yōu)配體,Ag_2CO_3為最適合的金屬,最好的溶劑和添加劑分別為甲苯和Et3N。然后分別在最優(yōu)條件下,對偶氮甲堿葉立德參與的[3+2]環(huán)加成反應(yīng)進(jìn)行了底物適應(yīng)性研究。結(jié)果表明,反應(yīng)具有非常好的底物適應(yīng)性,最多合成了33個不同取代的吡咯烷產(chǎn)物,并且得到了高達(dá)100%的非對映選擇性和98%的對映選擇性。(3)將單氨基酸衍生的膦酰胺配體應(yīng)用于異氰酸酯與醛的Aldol反應(yīng)。通過優(yōu)化金屬和溶劑找到最優(yōu)反應(yīng)條件,確定了最適宜的金屬和溶劑分別為Ag2O和乙酸乙酯。在篩選的最優(yōu)反應(yīng)條件下拓展了底物適應(yīng)性,合成了12個高取代的Aldol產(chǎn)物。并將該催化劑應(yīng)用于2-氨基-2-脫氧-D-果糖和2-脫氧-D-核糖的表全合成,選擇性高達(dá)93:7。此外,發(fā)展了一種以哌啶乙酸鹽為催化劑,催化鄰羥基苯基β-二酮和不同系列醛進(jìn)行Knoevenagel與O-Micheal串聯(lián)反應(yīng)的新方法,以較好的底物適應(yīng)性及中等以上的產(chǎn)率,合成了16個2,3-二取代苯并二氫吡喃-4-酮和9個2,2-二取代苯并呋喃-3-酮類衍生物,并研究了2,3-二取代-苯并二氫吡喃-4-酮與銪配位材料的熒光性能,合成了一類具有應(yīng)用前景的新型紅色熒光材料。
[Abstract]:In this thesis, the synthesized amino acids and cyclohexanediamine derived phosphonamide ligands were complexed with transition metals to form a new catalytic system. The catalytic system was applied to asymmetric [32] cycloaddition reaction. Ten phosphonamide ligands derived from single amino acid and six phosphine ligands derived from double amino acids were designed and synthesized from amino acids and cyclohexanediamine respectively. Cyclohexanediamine and amino acid derived phosphonamide ligands (4. 2) have been used to catalyze the asymmetric [32] cycloaddition reaction of azomethalide ylides with low electron olefins. The ligands and metals have been studied. The effects of solvents and additives on the catalytic performance of the catalyst were determined. The ligand 1gn1p and 1t were determined as the optimum ligands, Ag2COs _ 3 as the most suitable metal, toluene and et _ 3N as the best solvents and additives, respectively. The substrate adaptability of [32] cycloaddition reaction involving azonine ylide was studied. The results showed that the reaction had very good substrate adaptability, and at most 33 different substituted pyrrolidine products were synthesized. In addition, up to 100% enantioselectivity and 98% enantioselectivity were obtained. The phosphonamide ligands derived from single amino acid were applied to the Aldol reaction of isocyanate with aldehydes. The optimum reaction conditions were found by optimizing metal and solvent. The optimum metal and solvent were Ag2O and ethyl acetate respectively. The substrate adaptability was expanded under the optimum reaction conditions. Twelve highly substituted Aldol products were synthesized, and the catalyst was applied to the complete synthesis of 2-amino-2-deoxy--Dfructose and 2-deoxy--Dribose with selectivity up to 93: 7. In addition, a piperidine acetate catalyst was developed. A new method for the series reaction of Knoevenagel and O-Micheal catalyzed by o-hydroxyphenyl 尾 -diketone and different series of aldehydes was developed in order to obtain better substrate adaptability and moderate yield. Sixteen 2o 3-disubstituted benzodihydropyran-4-ketones and 9 2-disubstituted benzofuran -3-one derivatives were synthesized, and the fluorescence properties of 2O3-disubstituted benzodihydropyran-4-one coordination materials with europium were studied. A new kind of red fluorescent materials with application prospect has been synthesized.
【學(xué)位授予單位】：湖南工業(yè)大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：O641.4

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