钯碳催化Suzuki-Miyaura反应合成芳杂环取代三苯胺衍生物
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摘要
以芳杂环卤代物和4-硼酸三苯胺为原料,以Pd/C为催化剂,在乙醇水溶液中经Suzuki-Miyaura(SM)反应合成了芳杂环取代三苯胺衍生物。以2-溴吡啶与4-硼酸三苯胺的反应为模型反应,考察了溶剂、碱、温度及催化剂用量对反应的影响。得到的最优反应条件为:2-溴吡啶0.25mmol,4-硼酸三苯胺0.375mmol,Pd/C催化剂占2-溴吡啶的物质的量的1.5%,乙醇水溶液〔4 mL,V(乙醇)∶V(水)=3∶1〕,碳酸钾0.5 mmol,反应温度80℃,在该条件下合成了12个芳杂环取代三苯胺衍生物,产率为54%～99%,所有产物均通过核磁共振氢谱进行结构确认。该反应体系在空气及水相中进行且催化剂易于分离回收。
A heterogeneous catalytic system was developed for the synthesis of heteroaryl-substituted triphenylamine derivatives via a Pd/C-catalyzed aerobic and ligand-free Suzuki-Miyaura(SM)reaction of heteroaryl halides with 4-(diphenylamino)phenyl boronic acid(DPBA)in aqueous media.The reaction conditions(solvent,base,temperature and Pd/C loading)were optimized using a model cross-coupling reaction between 2-bromopyridine and DPBA.The optimal conditions were as follows:2-bromopyridine0.25 mmol,DPBA 0.375 mmol,the molar fraction of Pd/C in 2-bromopyridine being 1.5%,ethanol aqueous solution[4 mL,V(EtOH)∶V(H_2O)=3∶1],K_2CO_3 dosage 0.5 mmol,and reaction temperature 80℃.Under these optimal conditions,twelve triphenylamine derivatives were prepared with yields ranging from 54%to99%.The structures of the products were confirmed by ~1HNMR.The reaction was performed under aerobic and aqueous conditions,and the catalyst was easily separated and recovered.Therefore,this protocol is convenient and environmental benign for the preparation of important heteroaryl-substituted triphenylamine derivatives.
A heterogeneous catalytic system was developed for the synthesis of heteroaryl-substituted triphenylamine derivatives via a Pd/C-catalyzed aerobic and ligand-free Suzuki-Miyaura(SM)reaction of heteroaryl halides with 4-(diphenylamino)phenyl boronic acid(DPBA)in aqueous media.The reaction conditions(solvent,base,temperature and Pd/C loading)were optimized using a model cross-coupling reaction between 2-bromopyridine and DPBA.The optimal conditions were as follows:2-bromopyridine0.25 mmol,DPBA 0.375 mmol,the molar fraction of Pd/C in 2-bromopyridine being 1.5%,ethanol aqueous solution[4 mL,V(EtOH)∶V(H_2O)=3∶1],K_2CO_3 dosage 0.5 mmol,and reaction temperature 80℃.Under these optimal conditions,twelve triphenylamine derivatives were prepared with yields ranging from 54%to99%.The structures of the products were confirmed by ~1HNMR.The reaction was performed under aerobic and aqueous conditions,and the catalyst was easily separated and recovered.Therefore,this protocol is convenient and environmental benign for the preparation of important heteroaryl-substituted triphenylamine derivatives.
引文
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[14]Fang Z,Teo T L,Cai L,et al.Bridged triphenylamine-based dendrimers:tuning enhanced two-photon absorption performance with locked molecular planarity[J].Org Lett,2009,11(1):1-4.
[15]Walzer K,Maennig B,Pfeiffer M,et al.Highly efficient organic devices based on electrically doped transport layers[J].Chem Rev,2007,107(4):1233-1271.
[16]Hagfeldt A,Boschloo G,Sun L,et al.Dye-sensitized solar cells[J].Chem Rev,2010,110(11):6595-6663.
[17]Ono K,Joho M,Saito K,et al.Synthesis and electroluminescence properties offac-tris(2-phenylpyridine)iridium derivatives containing hole-trapping moieties[J].Eur J Inorg Chem,2006,(18):3676-3683.
[18]Lu J,Liu Q,Ding J,et al.New triscyclometalated iridium complexes for applications in phosphorescent light-emitting diodes[J].Synth Met,2008,158(3):95-103.
[19]Mak C S,Pentlehner D,Stich M,et al.Exceptional oxygen sensing capabilities and triplet state properties of Ir(ppy-NPh2)3[J].Chem Mater,2009,21(11):2173-2175.
[20]Marck G,Villiger A,Buchecker R.Aryl couplings with heterogeneous palladium catalysts[J].Tetrahedron Lett,1994,35(20):3277-3280.
[21]Felpin F X,Ayad T,Mitra S.Pd/C:An old catalyst for new applications:Its use for the Suzuki-Miyaura reaction[J].Eur J Org Chem,2006,(12):2679-2690.
[22]Seki M.Recent advances in Pd/C-catalyzed coupling reactions[J].Synthesis,2006,18:2975-2992.
[2]Miyaura N,Suzuki A.Palladium-catalyzed cross-coupling reactions of organoboron compounds[J].Chem Rev,1995,95(7):2457-2483.
[3]Sonogashira K,Tohda Y,Hagihara N.A convenient synthesis of acetylenes:Catalytic substitutions of acetylenic hydrogen with bromoalkenes,iodoarenes and bromopyridines[J].Tetrahedron Lett,1975,16(50):4467-4470.
[4]Nicolaou K C,Bulger P G,Sarlah D.Palladium-catalyzed crosscoupling reactions in total synthesis[J].Angew Chem Int Ed,2005,44(29):4442-4489.
[5]Miyaura N,Yamada K,Suzuki A.A new stereospecific crosscoupling by the palladium-catalyzed reaction of 1-alkenylboranes with1-alkenyl or 1-alkynyl halides[J].Tetrahedron Lett,1979,20(36):3437-3440.
[6]Wu X,Anbarasan P,Neumann H,et al.From noble metal to nobel prize:palladium-catalyzed coupling reactions as key methods in organic synthesis[J].Angew Chem Int Ed,2010,49(48):9047-9050.
[7]Johansson Seechurn C C,Kitching M O,Colacot T J,et al.Palladium-catalyzed cross-coupling:A historical contextual perspective to the 2010 nobel prize[J].Angew Chem Int Ed,2012,51(21):5062-5085.
[8]Han W,Liu C,Jin Z.In situ generation of palladium nanoparticles:a simple and highly active protocol for oxygen-promoted ligand-free Suzuki coupling reaction of aryl chlorides[J].Org Lett,2007,9(20):4005-4007.
[9]Liu C,Yang W.A fast and oxygen-promoted protocol for the ligand-free Suzuki reaction of 2-halogenated pyridines in aqueous media[J].Chem Commun,2009,(41):6267-6269.
[10]Yang W,Liu C,Qiu J.In situ formation of N,O-bidentate ligand via the hydrogen bond for highly efficient Suzuki reaction of aryl chlorides[J].Chem Commun,2010,46(15):2659-2661.
[11]Liu C,Han N,Song X,et al.A general and highly efficient method for the construction of aryl-substituted N-heteroarenes[J].Eur J Org chem,2010,(29):5548-5551.
[12]Liu C,Zhang Y,Liu N,et al.A simple and efficient approach for the palladium-catalyzed ligand-free Suzuki reaction in water[J].Green Chem,2012,14(11):2999-3003.
[13]Shirota Y,Kageyama H.Charge carrier transporting molecular materials and their applications in devices[J].Chem Rev,2007,107(4):953-1010.
[14]Fang Z,Teo T L,Cai L,et al.Bridged triphenylamine-based dendrimers:tuning enhanced two-photon absorption performance with locked molecular planarity[J].Org Lett,2009,11(1):1-4.
[15]Walzer K,Maennig B,Pfeiffer M,et al.Highly efficient organic devices based on electrically doped transport layers[J].Chem Rev,2007,107(4):1233-1271.
[16]Hagfeldt A,Boschloo G,Sun L,et al.Dye-sensitized solar cells[J].Chem Rev,2010,110(11):6595-6663.
[17]Ono K,Joho M,Saito K,et al.Synthesis and electroluminescence properties offac-tris(2-phenylpyridine)iridium derivatives containing hole-trapping moieties[J].Eur J Inorg Chem,2006,(18):3676-3683.
[18]Lu J,Liu Q,Ding J,et al.New triscyclometalated iridium complexes for applications in phosphorescent light-emitting diodes[J].Synth Met,2008,158(3):95-103.
[19]Mak C S,Pentlehner D,Stich M,et al.Exceptional oxygen sensing capabilities and triplet state properties of Ir(ppy-NPh2)3[J].Chem Mater,2009,21(11):2173-2175.
[20]Marck G,Villiger A,Buchecker R.Aryl couplings with heterogeneous palladium catalysts[J].Tetrahedron Lett,1994,35(20):3277-3280.
[21]Felpin F X,Ayad T,Mitra S.Pd/C:An old catalyst for new applications:Its use for the Suzuki-Miyaura reaction[J].Eur J Org Chem,2006,(12):2679-2690.
[22]Seki M.Recent advances in Pd/C-catalyzed coupling reactions[J].Synthesis,2006,18:2975-2992.