【作者】 王丽；

【导师】 龚军芳；

【作者基本信息】 郑州大学 ， 有机化学， 2012， 硕士

【摘要】 本文以手性氨基醇为手性源,合成了10种二甲基丙二酸衍生的手性双齿氮配体以及4种阳离子钳形铂化合物,对所合成的化合物进行了结构确证,并进一步考察了手性双齿氮配体在反式硝基烯烃和吲哚的不对称傅克烷基化反应及1,3-二羰基化合物和反式硝基烯烃的不对称迈克尔加成反应中的应用。主要内容如下：1.二甲基丙二酸衍生的手性双齿氮配体的合成与表征以二甲基丙二酸为起始原料,与氯化亚砜反应得到二甲基丙二酰氯,再与两倍量手性氨基醇反应得到双酰胺基醇,双酰胺基醇在氯化亚砜中加热回流发生氯化作用,蒸出氯化亚砜不经分离直接和伯胺搅拌反应24h之后,加入质量分数为15%的NaOH溶液搅拌数小时,得到1与2的混合物,1与2在NaOH存在条件下于THF-CH3OH中加热回流得到二甲基丙二酸衍生的手性双齿氮配体la-j (Scheme1)。化合物1a-j均为新化合物,并通过MS、HRMS、IR、1H NMR、13C NMR、HSQC等手段进行了表征。2.手性双齿氮配体在不对称傅克烷基化反应中的应用以反式硝基苯乙烯和吲哚的反应为模板反应,对反应条件进行了优化。优化了的反应条件为：以12mol%1a和10mol%Cu(OTf)2为催化剂,甲苯为反应溶剂,N2氛围下,吲哚与反式硝基苯乙烯5：1室温反应48h,在此条件下能够达到99%的收率和85%的ee值。在上述优化条件下对底物进行了拓展(Scheme2),取得了较好的催化效果,最高能达到98%的收率和88%的ee值,重结晶后ee值高达96%。3.手性双齿氮配体在不对称迈克尔加成反应中的应用以丙二酸二甲酯和反式硝基苯乙烯的反应为模板反应,对反应条件进行了优化。优化了的反应条件为：以12mol%1a和10mol%NiBr2为催化剂,甲苯为反应溶剂,丙二酸二甲酯与反式硝基苯乙烯2：1,N2氛围下反应48h,在此条件下能够达到86%的收率和80%的ee值。在上述优化条件下对底物进行了拓展(Scheme3),取得了良好的催化效果,最好得到94%的收率和81%的ee值。4.阳离子钳形铂化合物的合成与表征按照实验室已知的方法合成手性咪唑啉配体,以氯亚铂酸钾为铂源,通过直接金属化的方法得到NCN钳形铂氯化合物。钳形铂氯化合物在TlOTf存在下和水作用,得到阳离子钳形铂水化合物4a-b；钳形铂氯化合物在AgOTf存在下和吡啶反应,得到阳离子钳形铂吡啶化合物5b-c (Scheme4)。化合物3a,4a-b,5b-c均为新化合物,并通过MS、HRMS、IR、1H NMR、13C NMR、元素分析等手段进行了表征。初步尝试了阳离子钳形铂化合物在反式硝基苯乙烯和吲哚的不对称傅克烷基化反应中的应用,最高取得了80%的收率和60%的ee值。更多还原

【Abstract】 In this thesis, we have synthesized ten dimethylmalonic acid-derived chiral bidentate nitrogen ligands and four cationic pincer platinum complexes using chiral amino alcohols as the chiral sources. The new compounds were characterized by spectroscopic methods. The potential of the new ligands in the asymmetric Friedel-Crafts alkylation of nitroalkenes with indoles and Michael addition of1,3-dicarbonyl compounds to nitroalkenes were investigated. The main results are as follows:1. Synthesis and characterization of dimethylmalonic acid-derived chiral bidentate nitrogen ligandsTreatment of dimethylmalonic acid with SOC12gave dimethyl malonyldichloride, which reacted with2equiv. of optically active amino alcohol to afford the corresponding chiral amido alcohols. Then SOC12was added to amido alcohols and refluxed. After removal of excess SOC12under reduced pressure, amines were added and stirred for24h, followed by addition of15%aqueous NaOH. The obtained mixture of1and2was refluxed in THF-CH3OH in the presence of NaOH to produce chiral bidentate nitrogen ligands la-j (Scheme1). la-j were new compounds, which were characterized by MS, HRMS, IR,1H NMR,13C NMR, HSQC spectra.2. Applications of chiral bidentate nitrogen ligands in the asymmetric Friedel-Crafts alkylationTrans-β-nitrostyrene was chosen to react with indole for optimizing reaction conditions. The optimal reaction conditions are as follows:trans-β-nitrostyrene reacted with indole (1:5) in the presence of10mol%Cu(OTf)2/12mol%1a in toluene at room temperature for48h under N2atmosphere, giving the product in an excellent yield (99%) and good enantioselectivity (85%ee). The reactions of a variety of nitroalkenes and indoles were investigated under the optimal conditions (Scheme2). It was found that the nitroalkylated indoles were obtained with excellent yields (up to98%) and high enantioselectivities (up to88%ee, up to96%ee after recrystallization).3. Applications of chiral bidentate nitrogen ligands in the asymmetric Michael additionDimethyl malonate was chosen to react with trans-β-nitrostyrene for optimizing reaction conditions. The optimal reaction conditions are as follows:dimethyl malonate reacted with trans-β-nitrostyrene (2:1) in the presence of10mol%NiBr2/12mol%1a in toluene for48h under N2atmosphere, affording the product in a good yield (86%) and good enantioselectivity (80%ee). The reactions of a variety of nitroalkenes and1,3-dicarbonyl compounds were investigated under the optimized conditions (Scheme3) and the addition products were obtained with up to94%yield and81%ee.4. Synthesis and characterization of cationic pincer platinum complexesWe synthesized chiral imidazoline ligands according to the method reported by us, which reacted with K2PtCl4by direct cyclometalation to produce the neutral NCN pincer chloroplatinum complexes. The cationic platinum aquo complexes4a-b were prepared by the reaction of Pt-Cl complexes with H2O in the presence of TlOTf. The cationic platinum pyridine complexes5b-c were prepared by the reaction of Pt-Cl complexes with pyridine in the presence of AgOTf (Scheme4).3a,4a-b,5b-c were new compounds, which were characterized by MS, HRMS, IR,1H NMR,13C NMR and elemental analysis. The cationic pincer platinum complexes were applied to the asymmetric Friedel-Crafts alkylation of indole with trans-β-nitrostyrene, affording the product with up to80%yield and60%ee.更多还原