(S)-BINAM衍生的新型吡啶-硫脲双功能有机催化剂的合成

Synthesis of a novel( S)-BINAM-derivated pyridine-thiourea bifunctional organocatalyst

新型吡啶-硫脲双功能有机催化剂(Ⅳ),由(S)-1,1-联二萘胺(Ⅰ)和2-溴吡啶在80℃条件下经BuchwaldHartwig偶联反应,以60%的收率得到中间体(Ⅱ);随后以吡啶为缚酸剂,三氟乙胺、硫代氯甲酸-4-硝基苯酯在二氯甲烷中于室温下反应10 min,向反应体系中加入中间体(Ⅱ)及DIPEA继续于室温下反应12 h,即可以70%的收率获得催化剂(Ⅳ)。其结构经1H NMR和13C NMR进行了表征。

A novel pyridine-thiourea bifunctional organocatalyst has been developed. The intermediate（ Ⅱ） was synthesized by the Buchwald-Hartwig coupling reaction of（ S）-2,2＇-diamino-1,1＇-binaphthalene and 2-bromopyridine under the condition of 80 ℃ with up to 60% yield. And then we used pyridine as base,trifluoroethylamine and 4-nitrophenyl chlorothionoformate in dichloromethane were stirred at room temperature for 10 min,subsequently added the intermediate（ Ⅱ） and DIPEA to the reaction system,which was continued for another 12 h at room temperature,at last the catalyst（ Ⅳ） can be obtained in70% yield,and the structure was characterized by1 H NMR,13 C NMR.