腺嘌呤改性环糊精及绿色催化Suzuki偶联反应研究  

Study on Adenine-Modified Cyclodextrin and Green Catalytic Suzuki Coupling Reaction

作　　者：李瑞 张东东 周多 周诗雨 郭旭明[1] LI Rui;ZHANG Dongdong;ZHOU Duo;ZHOU Shiyu;GUO Xuming(College of Chemical Engineering and Pharmaceutics, Henan University of Science and Technology, Luoyang 471023, China)

机构地区：[1]河南科技大学化工与制药学院,河南洛阳471023

出　　处：《合成化学》2022年第7期527-533,共7页Chinese Journal of Synthetic Chemistry

基　　金：河南省国际科技合作计划项目(134500510034);河南省科技攻关项目(222102320065)。

摘　　要：以腺嘌呤与β-环糊精(β-cyclodextrin,β-CD)为原料,首次合成了单-(6-腺嘌呤-6-脱氧)-β-CD。采用红外(IR),紫外(UV),核磁共振(NMR)和电喷雾质谱(ESI-MS)对单-(6-腺嘌呤-6-脱氧)-β-CD的结构进行了表征。首次以单-(6-腺嘌呤-6-脱氧)-β-CD为配体,醋酸钯(Pd(OAc)_(2))为钯源,高效原位催化了水相Suzuki偶联反应。探索了催化剂用量、缚酸剂种类、四丁基溴化铵(TBAB)用量、反应温度、反应时间等因素对催化反应的影响,研究了催化反应的底物普适性。结果表明:以对溴甲苯和苯硼酸为底物,K_(3)PO_(4)·7H_(2)O为缚酸剂,TBAB为相转移催化剂,在单-(6-腺嘌呤-6-脱氧)-β-CD与醋酸钯的物质的量比为4∶1,催化剂物质的量分数为0.030 mol/mol条件下,80℃反应2 h时,对溴甲苯几乎可以完全转化。而在优化后的催化条件下,溴代及含有吸电子取代基的氯代芳烃底物普适性较好,偶联反应产率均在85%以上。该催化反应具有腺嘌呤衍生β-环糊精合成简单,成本低,偶联反应可在水相中进行,催化剂用量少,反应时间短等优点。Mono-(6-adenine 6-deoxy)-β-CD was first synthesized from adenine andβ-cyclodextrin(β-CD).The structure of mono-(6-adenine-6-deoxy)-β-CD was characterized by infrared(IR),ultraviolet(UV),nuclear magnetic resonance(NMR)and electrospray ionization mass spectrometry(ESI-MS).Using it as ligand and palladium acetate(Pd(OAc)_(2))as palladium source,which can efficiently catalyzed the aqueous phase Suzuki coupling reaction in situ.The effects of the amount of catalyst,the type of acid binding agent,the amount of tetrabutylammonium bromide(TBAB),reaction temperature and reaction time on the catalytic reaction were investigated,and the universality of the substrate of the catalytic reaction was studied.The results show that p-bromotoluene can be converted almost completely when p-bromotoluene and phenylboric acid are used as substrates,molar ratio of mono-(6-adenine-6-deoxy)-β-CD to Pd(OAc)_(2) is 4∶1,K_(3)PO_(4)·7H_(2)O as acid-binding agent and TBAB as phase transfer catalyst when the mass fraction of catalyst is 0.030 mol/mol and reacts at 80℃for 2 h.Under the optimized catalytic conditions,the universality of various aryl bromides and aryl chlorides containing electron-withdrawing groups is very good,and the yield of Suzuki carbon-carbon cross-coupling reaction can reach more than 85%.The catalytic reaction of adenine derivedβ-CD has the advantages of simple synthesis,low cost,coupling reaction in water phase,less catalyst and short reaction time.

关 键 词：Β-环糊精 单-(6-腺嘌呤-6-脱氧)-β-CD 腺嘌呤 水相催化 SUZUKI偶联反应 绿色合成 

分 类 号：O641.3[理学—物理化学]