联芳骨架手性双咪唑啉配体的合成及其在不对称傅克烷基化反应中的应用-有机化学专业论文.docxVIP

摘要 摘要 万方数据 万方数据 Scheme 2 2. 手性配体 8a-f 在不对称傅克烷基化反应中的应用 以吲哚和反式硝基苯乙烯为模板反应(Scheme 3)，对所制备手性配体不对 称诱导性质进行探索。通过反应条件的筛选，得到的优化反应条件为：一倍量 吲哚，二倍量的反式硝基苯乙烯，10 mol% Zn(OTf)2，11 mol% 8d，CH2Cl2 为 溶剂，氩气保护，40 oC 反应 48 h，在优化条件下以 98%的收率和 37%的 ee 值 吲哚和反式硝基苯乙烯反应的产物。接着探究了吲哚与带有不同取代基的硝基 烯在以上条件下的反应情况，得到了良好的催化结果，收率高达 99%，ee 值最 高可达 57%。 Scheme 3 关键词：联芳；双咪唑啉；手性配体；不对称傅克烷基化 II Abst Abstract Abstract This paper discusses the synthesis and characterization of chiral bisimidazoline ligands with biaryl backbones and their application in the asymmetric Friedel-Crafts alkylation of indoles with nitroalkenes. The main research contents are as follows: Synthesis of chiral ligands 8d-f 3,5-Dimethyl benzoic acid reacted with bromine to get 2-bromine-3,5-dimethyl benzoic acid 5a. Then compound 5a and 5b respectively reacted with SOCl2 , followed by reacting with amino alcohols at room temperature in the presence of Et3N in CH2Cl2, to afford the corresponding amido alcohols 6a-f. Final products 7a-f were obtained from compounds 6a-f and primary amine, as shown in scheme 1. The new compounds 6a-c , 7a-c were all fully characterized by 1H NMR, 13C NMR, IR and HRMS. Scheme 1 The axially chiral ligands 8a-c were obtained from a mixture of 7a-c and freshly activated copper in dry DMF which were heated at reflux under argon atmosphere for 24 h (Scheme 2). Single diastereomers 8a-c were obtained after III isolated from column chromatography. The new compounds 8a-c were all fully characterized by 1H NMR, IR, 13C NMR and HRMS. Scheme 2 The application of ligands 8a-f in the asymmetric Friedel-Crafts alkylation reactions. We investigated the application of compounds 8a-f as chiral catalyst in the asymmetric Friedel-Crafts alkylation reactions of trans-nitrostyenes and indoles (Scheme 3). The optimized reaction condition sited as 10 mol% Zn(OTf)2, 11 mol% 8d, in CH2Cl2 at 40 oC for 48 h under argon atmosphere, giving the product in a good yield (98%) and moderate enantioselectivity (37% ee). We then explored th