邻氨基苯甲酸改性β-环糊精的合成及钯催化水相Heck偶联反应
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摘要
以邻氨基苯甲酸与β-环糊精(β-CD)为原料,合成了单-(6-邻氨基苯甲酸-6-脱氧)-β-CD。采用核磁共振氢谱(~1H NMR)和核磁共振碳谱(~(13)C NMR)对单-(6-邻氨基苯甲酸-6-脱氧)-β-CD进行了表征,以其为配体,醋酸钯(Pd(OAc)_2)为钯源,高效原位催化了水相Heck偶联反应。探索了催化剂用量、缚酸剂、温度、反应时间对催化反应的影响,并分析了催化反应的底物普适性。试验结果表明:以碘苯和苯乙烯为底物,K_2CO_3为缚酸剂,当催化剂物质的量分数为0.20%时,130℃反应10 h,碘苯几乎可以完全转化。在最优催化条件下,底物的偶联产率可达80%以上,底物的空间位阻及电子效应对产率有一定的影响。
Taking o-amino benzonic acid andβ-CD as raw materials,mono-(6-o-amino benzonic acid-6-deoxy)-β-CD was synthesized and characterized by~1H NMR and~(13)C NMR.Heck coupling reaction was proceeded with high efficiency in aqueous media by using mono-(6-o-amino benzonic acid-6-deoxy)-β-CD as the ligand and palladium acetate as the palladium source.The effects of catalyst loadings,bases,reaction temperature and reaction time on Heck coupling reaction were explored,and the scope of the substrates was analyzed.The results show iodobenzene can almost be converted totally by utilizing iodobenzene and styrene as substrates,K_2CO_3as the base,with 0.20%of the catalyst loading,at 130℃for 10 h.Under the optimized reaction conditions,the coupling yields of the substrates can be above 80%and the yields are influenced by the steric hinderance and electronic effect.
Taking o-amino benzonic acid andβ-CD as raw materials,mono-(6-o-amino benzonic acid-6-deoxy)-β-CD was synthesized and characterized by~1H NMR and~(13)C NMR.Heck coupling reaction was proceeded with high efficiency in aqueous media by using mono-(6-o-amino benzonic acid-6-deoxy)-β-CD as the ligand and palladium acetate as the palladium source.The effects of catalyst loadings,bases,reaction temperature and reaction time on Heck coupling reaction were explored,and the scope of the substrates was analyzed.The results show iodobenzene can almost be converted totally by utilizing iodobenzene and styrene as substrates,K_2CO_3as the base,with 0.20%of the catalyst loading,at 130℃for 10 h.Under the optimized reaction conditions,the coupling yields of the substrates can be above 80%and the yields are influenced by the steric hinderance and electronic effect.
引文
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[4]ZHOU M,CAI S T,LI J,et al.High-efficiency and magnetically separable nanocatalyst:beta-cyclodextrin modified coreshell hybrid magnetic nanoparticles[J].Journal of inclusion phenomena and macrocyclic chemistry,2017,87(1/2):45-51.
[5]FRENCH R R,HOLZER P,LEUENBERGER M,et al.A supramolecular enzyme model catalyzing the central cleavage of carotenoids[J].Journal of inorganic biochemistry,2002,88(3/4):295-304.
[6]BONCHIO M,CAROFIGLIO T,DIFURIA F,et al.Supramolecular catalysis-enantioselective oxidation of thioannisole in water by hydrogen-peroxide catalyzed by Mo(VI)in the presence of beta-cyclodextrin-based ligands[J].Journal of organic chemistry,1995,60(18):5986-5988.
[7]KHOURI S I J,ALTWAIQ A.Deceleration the hydrolysis reaction of ethyl acetate ester by beta-cyclodextrin in basic medium:transition state analog[J].Journal of inclusion phenomena and macrocyclic chemistry,2017,87(3/4):305-311.
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[9]KAIROUZ V,SCHMITZER A R.Imidazolium-functionalized beta-cyclodextrin as a highly recyclable multifunctional ligand in water[J].Green chemistry,2014,16(6):3117-3124.
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[15]HONG S,LIU M,SHUAI Y,et al.Amino acid-modified cyclodextrins as ligands for Heck reaction in water[J].Journal of inclusion phenomena and macrocyclic chemistry,2014,80(3/4):443-448.
[16]DINDULKAR S D,JEONG D,KIM H,et al.Functionalized beta-cyclodextrin as supramolecular ligand and their Pd(OAc)2complex:highly efficient and reusable catalyst for Mizoroki-Heck cross-coupling reactions in aqueous medium[J].Carbohydrate research,2016,430:85-94.
[17]ARSALANI N,AKBARI A,AMINI M,et al.Poss-based covalent networks:supporting and stabilizing Pd for Heck reaction in aqueous media[J].Catalysis letters,2017,147(4):1086-1094.