镓试剂催化的C-N成键反应研究
摘要
三氟甲磺酸镓是一个稳定、可循环利用的强路易斯酸催化剂,它易溶于水、乙醇、甲醇、乙腈等极性溶剂,是一个理想的有机反应催化剂。高氯酸锂与硝基甲烷(LPNM)体系常作为一种助催化剂出现在三氟甲磺酸盐的催化反应中,LPNM的加入可使三氟甲磺酸盐催化的付克反应效率显著提升,但迄今为止该体系的应用仅停留在付克反应上。高氯酸镓作为有机反应催化剂的应用尚未报道,我们的研究表明它能有效催化C-N键的形成。
本论文分为三个部分:第一部分介绍了三氟甲磺酸镓催化的邻苯二胺与炔酮的成环反应,高产率合成了二氮杂卓类衍生物。该反应在95%乙醇中进行,催化剂用量少,并且可以反复使用10次以上而产率没有明显降低。第二部分介绍了LPNM体系促进的C-N成键反应,研究发现可选择性的得到N-烷基化、单分子付克反应和双分子付克反应产物。该过程先后经历了C-N键的形成、付克反应、C-N键的断裂和新的C-C键的形成。第三部分介绍了高氯酸镓催化的C-N成键反应。所有产物的结构得到了核磁共振谱、质谱等的证实。
Gallium triflate is a stable reusable Lewis acid catalyst which can easily dissolve in polar solvents such as water, EtOH, MeOH, CH3CN. It is a versatile catalyst. As a co-catalyst commonly accompanied with metal triflates, application of LPNM (LiClO4-CH3NO2) for catalysis effect mainly lied in the Fridel-Crafts reaction currently. Gallium perchlorate is never reported for organic reactions, but our study confirms its usage in C-N formation which reflects its catalytical power.
This thesis contains three parts. Firstly, we studied the catalytic properties of gallium triflate, which could efficiently catalyze the condensation of o-phenylenediamines and ynones to form bioactive 1, 5-benzodiazepines in good yields. This reaction was conducted under 95% ethanol at room temperature and the gallium catalyst could be recovered for 10 times without a drastically diminishment of catalytical effect which highlighted our catalyst as a green catalyst. Secondly, a direct way to build up C-N bond in LPNM medium was introduced and chemoselectivity was successfully achieved to attain N-Alkylated or Mono and Double Friedel-Crafts products. The whole process proceeded through the formation of C-N bond, Fridel-Crafts reaction, break of C-N bond and the sequent C-C bond formation. Finally, we did a futher study in C-N bond formation catalyzed by gallium perchlorate. All the products were confirmed by 1H NMR, 13C NMR and HRMS analysis.
本论文分为三个部分:第一部分介绍了三氟甲磺酸镓催化的邻苯二胺与炔酮的成环反应,高产率合成了二氮杂卓类衍生物。该反应在95%乙醇中进行,催化剂用量少,并且可以反复使用10次以上而产率没有明显降低。第二部分介绍了LPNM体系促进的C-N成键反应,研究发现可选择性的得到N-烷基化、单分子付克反应和双分子付克反应产物。该过程先后经历了C-N键的形成、付克反应、C-N键的断裂和新的C-C键的形成。第三部分介绍了高氯酸镓催化的C-N成键反应。所有产物的结构得到了核磁共振谱、质谱等的证实。
Gallium triflate is a stable reusable Lewis acid catalyst which can easily dissolve in polar solvents such as water, EtOH, MeOH, CH3CN. It is a versatile catalyst. As a co-catalyst commonly accompanied with metal triflates, application of LPNM (LiClO4-CH3NO2) for catalysis effect mainly lied in the Fridel-Crafts reaction currently. Gallium perchlorate is never reported for organic reactions, but our study confirms its usage in C-N formation which reflects its catalytical power.
This thesis contains three parts. Firstly, we studied the catalytic properties of gallium triflate, which could efficiently catalyze the condensation of o-phenylenediamines and ynones to form bioactive 1, 5-benzodiazepines in good yields. This reaction was conducted under 95% ethanol at room temperature and the gallium catalyst could be recovered for 10 times without a drastically diminishment of catalytical effect which highlighted our catalyst as a green catalyst. Secondly, a direct way to build up C-N bond in LPNM medium was introduced and chemoselectivity was successfully achieved to attain N-Alkylated or Mono and Double Friedel-Crafts products. The whole process proceeded through the formation of C-N bond, Fridel-Crafts reaction, break of C-N bond and the sequent C-C bond formation. Finally, we did a futher study in C-N bond formation catalyzed by gallium perchlorate. All the products were confirmed by 1H NMR, 13C NMR and HRMS analysis.
引文
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