NCN钳形铱化合物催化重氮化合物与1,4-环己二烯的不对称C-H键插入反应

发布时间：2018-07-20 12:09

【摘要】：本论文通过实验室已有的合成方法制备了一系列手性双(咪唑啉)苯NCN钳形铱(III)化合物,并探究了其在重氮化合物与1,4-环己二烯的不对称C-H插入反应中的催化活性,主要实验结果如下:1.手性双(咪唑啉)苯NCN钳形铱(III)化合物的合成根据实验室已报道的方法以商品化的5-叔丁基间苯二甲酸为起始原料,经过羧基与二氯亚砜反应转化为酰氯;酰氯与手性氨基醇反应,得到酰胺基醇;而后,酰胺基醇依次在二氯亚砜、胺、氢氧化钠作用下经历三步反应得到了相应的手性的双(咪唑啉)苯配体1a-g;最后将化合物1a-g与三水合三氯化铱反应,经过中心芳环的C-H键活化法得到钳形铱-氯化合物[(Phebim)Ir Cl2(H2O)]2a-g(Scheme 1)。2.手性NCN钳形铱(III)化合物催化α-芳基重氮酯类化合物与1,4-环己二烯的不对称C-H键插入反应本论文探索了手性钳形铱(III)化合物在芳基重氮乙酸酯与1,4-环己二烯的不对称C-H插入反应中的催化性能。通过对催化剂2a-g以及温度的筛选得到了反应的最优条件,达到79%的产率和96%的ee值(Scheme 2)。并在优化条件下进行了底物扩展。因为所得产品为已知化合物,所以其结构仅通过核磁氢谱确定即可。3.手性NCN钳形铱(III)化合物催化3-重氮吲哚类化合物与1,4-环己二烯的不对称C-H键插入反应本论文继续探索了手性钳形铱化合物在3-重氮-1,3-二氢-2-羰基吲哚类化合物与1,4-环己二烯的不对称C-H插入反应中的催化性能。通过对催化剂用量、温度、溶剂等的筛选获得了最佳反应条件,可达到88%的产率和93%的ee值,并在最优条件下扩展了14个底物。所得到的新化合物结构经过了核磁氢谱、碳谱、氟谱以及高分辨质谱的表征,产物的绝对构型也通过单晶X-射线衍射法得以确定(Scheme 3)。
[Abstract]:In this paper, a series of chiral bis (Imidazoline) phenylNCN forceps iridium (III) compounds were prepared by the existing synthetic methods in laboratory, and their catalytic activity in the asymmetric C-H insertion reaction of diazo compounds with 1o 4-cyclohexadiene was investigated. The main experimental results are as follows: 1. Synthesis of Chiral Bis (Imidazoline) phenylNCN clamp Iridium (III) compounds according to the methods reported in the laboratory, the commercial 5- tert Ding Ji isophthalic acid was used as the starting material and the carboxyl group reacted with dichloro sulfoxide to convert to acyl chloride. Acyl chloride reacts with chiral amino alcohols to obtain amino-alcohols, and then, amino-alcohols are followed by dichloro sulfoxide, amines, amines, The chiral bis (Imidazoline) benzene ligand 1a-g was obtained by the three-step reaction of sodium hydroxide. Finally, the compound 1a-g was reacted with iridium trichloride, and the clamped iridium chloride compound [(Phebim) ir Cl 2 (H 2O)] 2a-g (Scheme 1) .2was obtained by C-H bond activation of the central aromatic ring. Asymmetric C-H bond insertion reaction of 伪 -aryl diazoates with 1o _ 4-cyclohexadiene catalyzed by chiral NCN forceps iridium (III) compounds in the presence of aryl diazoacetate and 1o _ 4-cyclohexadiene The catalytic activity of C-H insertion reaction is called. The optimum reaction conditions were obtained by screening the catalyst 2a-g and temperature. The yield was 79% and the ee value was 96% (Scheme 2). The substrate expansion was carried out under the optimized conditions. Because the product is a known compound, its structure can only be determined by nuclear magnetic hydrogen spectrum. 3. Asymmetric C-H bond insertion reaction of 3-diazoindole compounds with 1-diazo4-cyclohexadiene catalyzed by chiral NCN forceps iridium (III). In this paper, chiral forceps iridium compounds in the presence of 3-diazo-1-dihydro-3-dihydro-2-carbonyl indoles were investigated. The catalytic properties of asymmetric C-H insertion reaction of 1: 4-cyclohexadiene. The optimum reaction conditions were obtained by screening the amount of catalyst, temperature, solvent and so on. The yield of 88% and ee value of 93% were obtained, and 14 substrates were expanded under the optimum conditions. The structures of the new compounds were characterized by nuclear magnetic hydrogen spectroscopy, carbon spectrum, fluorine spectrum and high resolution mass spectrometry. The absolute configuration of the product was also determined by single crystal X-ray diffraction (Scheme 3).
【学位授予单位】：郑州大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：O621.251

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