过渡金属与多官能磷配体配位特点及应用研究

发布时间：2018-03-04 01:36

本文选题：手性膦配体　切入点：偶氮甲碱叶立德　出处：《湖南工业大学》2017年硕士论文　论文类型：学位论文

【摘要】：本论文将设计合成的氨基酸和环己二胺衍生的膦酰胺配体与过渡金属络合,形成新的催化体系,并将该催化体系应用于不对称[3+2]环加成反应的研究。(1)以氨基酸和环己二胺为原料,分别设计合成了单氨基酸衍生的膦酰胺配体10个,双氨基酸衍生的膦配体6个,环己二胺和氨基酸衍生的膦酰胺配体4个。(2)将上述不同骨架的膦酰胺配体用于催化偶氮甲碱叶立德与贫电子烯烃的不对称[3+2]环加成反应。研究了配体、金属、溶剂和添加剂对催化剂催化性能的影响。确定了配体1g,1p和1t为最优配体,Ag_2CO_3为最适合的金属,最好的溶剂和添加剂分别为甲苯和Et3N。然后分别在最优条件下,对偶氮甲碱叶立德参与的[3+2]环加成反应进行了底物适应性研究。结果表明,反应具有非常好的底物适应性,最多合成了33个不同取代的吡咯烷产物,并且得到了高达100%的非对映选择性和98%的对映选择性。(3)将单氨基酸衍生的膦酰胺配体应用于异氰酸酯与醛的Aldol反应。通过优化金属和溶剂找到最优反应条件,确定了最适宜的金属和溶剂分别为Ag2O和乙酸乙酯。在筛选的最优反应条件下拓展了底物适应性,合成了12个高取代的Aldol产物。并将该催化剂应用于2-氨基-2-脱氧-D-果糖和2-脱氧-D-核糖的表全合成,选择性高达93:7。此外,发展了一种以哌啶乙酸盐为催化剂,催化邻羟基苯基β-二酮和不同系列醛进行Knoevenagel与O-Micheal串联反应的新方法,以较好的底物适应性及中等以上的产率,合成了16个2,3-二取代苯并二氢吡喃-4-酮和9个2,2-二取代苯并呋喃-3-酮类衍生物,并研究了2,3-二取代-苯并二氢吡喃-4-酮与铕配位材料的荧光性能,合成了一类具有应用前景的新型红色荧光材料。
[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.
【学位授予单位】：湖南工业大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O641.4

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