【作者】 王嘉；

【导师】 渠瑾；

【作者基本信息】 南开大学 ， 有机化学， 2011， 硕士

【摘要】 本论文分为两部分。在第一部分工作中,我们发展了在沸水中,对杂环上的N原子,脂肪胺,以及芳香胺类化合物的N-Boc保护基进行脱除的反应体系。大多数在水中溶解性较好的胺类化合物的N-Boc保护基都能在我们的这一体系中得到有效地脱除。对组胺,色胺这样的具有两种不同类型的氨基的化合物来说,可以选择性地实现只脱除反应活性更高的杂环N原子上的N-Boc保护基。我们认为水在N-Boc保护基的脱除反应中起到了酸碱共催化剂的作用,N-Boc底物的分解最终产物为对应的胺类化合物和叔丁醇。和已报道的其他的N-Boc脱除反应体系相比,我们的反应体系更加绿色环保。在第二部分工作中,我们以手性BINOL为骨架,合成了一系列3,3’位具有不同取代基团的手性磷酸催化剂,并对吲哚与2,2,2-三氟苯丙酮之间的F-C反应,L-半胱氨酸与硝基苯乙烯之间的Michael加成反应以及3,5-二羟基苯酚与亚胺之间的F-C反应这三个不对称催化反应进行了初步的探索。更多还原

【Abstract】 This thesis contains two parts.In the first part, we developed a method using boiling water as reaction media to remove Boc protecting group on heterocyclic aromatic amines, aliphatic amines and aromatic amines. In most of the cases, the N-Boc group on the substrate which bearing good solubility in water can be removed effectively in our system. For substrates like di-Boc histamine and di-Boc tryptophan amine, only the Boc group linked to more reactive heterocyclic aromatic amine can be removed, if the reaction was stopped at certain point. We suppose water functions as dual acid/base catalyst in our reaction system. The final decomposition compound of the N-Boc substrate was amine and t-butyl alcohol. Our reaction system is greener than those other reported N-Boc deprotection methods.In the second part, we synthesized several BINOL based chiral phosphorous catalysts bearing various substitute group at 3,3’position and put them into preliminary research on asymmetric catalysis. Our tested asymmetric reactions include:1) F-C reaction between indole and 2,2,2-trifluoro-1-phenylethanone; 2) Michael addition between L-Cystein and (E)-(2-nitrovinyl) benzene; 3) F-C reaction between 3,5-dimethoxyphenol and imine.更多还原