钯纳米颗粒负载在聚苯胺材料上制得催化Suzuki-Miyaura偶联反应的高效催化剂（英文）
|
摘要
在最近的几十年里,金属钯催化的Suzuki-Miyaura偶联反应已经得到了越来越多的关注,被广泛应用于药物、天然产物以及新材料的合成.与此同时均相催化剂发展迅速,高效的配体和大量的设计被用于Suzuki-Miyaura偶联反应中,但是钯催化剂的配体通常很昂贵和难以合成,因此钯催化剂系统的回收是非常有价值的,不仅是经济上的原因,同时也避免了产品的污染,所以发展非均相催化剂是必要的.近年来,研究学者们致力于设计非均相的钯催化剂,如将钯纳米颗粒负载到金属有机骨架、介孔分子筛以及活性炭等多种材料上得到的非均相钯催化剂并应用于Suzuki-Miyaura偶联反应中.我们主要介绍了钯纳米颗粒被负载在含磷配体的交联的聚苯胺材料上制得负载的钯催化剂,首先通过钯催化的三(4-碘苯基)胺与金刚烷基膦的C–P偶联,再由钯催化三(4-碘苯基)胺与对苯二胺的C–N偶联,进而得到钯纳米颗粒负载在含金刚烷基膦的聚苯胺材料上的催化剂Pd@PAN-Ad-0.5(钯含量为0.58 wt%),同时我们对催化剂进行了一些表征,如TEM,SEM,XRD,EDX,XPS,FT-IR,ICP等.通过TEM分析,我们发现钯纳米颗粒在聚合物表面分布均匀,并且金属钯的平均粒径为2–3 nm;EDX检测显示催化剂含有C,N,P,Pd,I元素,说明钯负载到含金刚烷基膦的聚苯胺材料上的催化剂Pd@PAN-Ad-0.5已经形成,并被用于Suzuki-Miyaura偶联反应.我们对反应体系中的各种影响因素进行了优化,包括溶剂、碱、反应时间、催化剂加入量以及不同的催化剂的优化,最终确定了最佳反应条件;对于带有不同取代基(如腈基、甲氧基、醛基、酮基以及硝基)的氯代芳烃和溴代芳烃与苯硼酸的Suzuki-Miyaura反应,以较少的催化剂使用量(0.075 mol%Pd)就能获得较高的相应的联苯产物收率.此外,催化剂Pd@PAN-Ad-0.5在偶联反应中具有较高的反应活性的同时,还具有较好的回收使用能力(至少能够回收使用5次),循环使用4次以后还具有较高的催化活性.为了探索催化剂Pd@PAN-Ad-0.5在工业上的应用,由于4'-氯-2-硝基-1,1'-联苯是合成啶酰菌胺药物的重要中间体,因此我们使用催化剂Pd@PAN-Ad-0.5催化2-硝基氯苯与4-氯苯硼酸的偶联反应,目标产物4'-氯-2-硝基-1,1'-联苯的收率高达96%.我们相信这类催化剂应用于实验室或工业上合成联苯化学品具有较大的潜力.
Palladium nanoparticles supported on cross-linked polyaniline with bulky phosphorus ligands were developed.These catalysts showed high efficiency in the Suzuki-Miyaura reaction of aryl chlorides and bromides with phenylboronic acids.Aryl chlorides and bromides with functional groups,such as CN,MeO,CHO,MeCO and NO_2,were converted to the corresponding biphenyls in high yields with catalyst loading.Additionally,the catalysts combined high activity with good reusability;they could be used at least five times for the Suzuki-Miyaura coupling reaction.
Palladium nanoparticles supported on cross-linked polyaniline with bulky phosphorus ligands were developed.These catalysts showed high efficiency in the Suzuki-Miyaura reaction of aryl chlorides and bromides with phenylboronic acids.Aryl chlorides and bromides with functional groups,such as CN,MeO,CHO,MeCO and NO_2,were converted to the corresponding biphenyls in high yields with catalyst loading.Additionally,the catalysts combined high activity with good reusability;they could be used at least five times for the Suzuki-Miyaura coupling reaction.
引文
[1]C.C.C.Johansson Seechurn,M.O.Kitching,T.J.Colacot,V.Snieck-us,Angew.Chem.Int.Ed.,2012,51,5062-5085.
[2]A.J.J.Lennox,G.C.Lloyd-Jones,Chem.Soc.Rev.,2014,43,412-443.
[3]J.K.Wang,Y.X.Zong,X.C.Wang,Y.L.Hu,G.R.Yue,Y.Pan,Green Chem.,2016,18,967-973.
[4]G.D.Ding,W.T.Wang,T.Jiang,B.X.Han,Green Chem.,2013,15,3396-3403.
[5]A.Molnar,Chem.Rev.,2011,111,2251-2320.
[6]J.F.Hartwig,Nature,2008,455,314-322.
[7]A.Fihri,M.Bouhrara,B.Nekoueishahraki,J.M.Basset,V.Polshet-tiwar,Chem.Soc.Rev.,2011,40,5181-5203.
[8]N.Miyaura,A.Suzuki,Chem.Rev.,1995,95,2457-2483.
[9]S.Paul,M.M.Islam,S.M.Islam,RSC Adv.,2015,5,42193-42221.
[10]P.Das,W.Linert,Coord.Chem.Rev.,2016,311,1-23.
[11]R.Garrido,P.S.Hernandez-Montes,A.Gordillo,P.Gomez-Sal,C.Lopez-Mardomingo,E.de Jesus,Organometallics,2015,34,1855-1863.
[12]Y.Nakayama,N.Yokoyama,H.Nara,T.Kobayashi,M.Fujiwhara,Adv.Synth.Catal.,2015,357,2322-2330.
[13]N.Dehury,N.Maity,S.K.Tripathy,J.M.Basset,S.Patra,ACS Catal.,2016,6,5535-5540.
[14]L.C.Lee,J.He,J.Q.Yu,C.W.Jones,ACS Catal.,2016,6,5245-5250.
[15]S.Roy,H.Plenio,Adv.Synth.Catal.,2010,352,1014-1022.
[16]W.Q.Fu,Y.Feng,Z.X.Fang,Q.Chen,T.Tang,Q.Y.Yu,T.D.Tang,Chem.Commun.,2016,52,3115-3118.
[17]J.X.Yang,X.M.Tan,Y.Wang,X.H.Wang,J.Porous Mater.,2013,20,501-506.
[18]F.Wang,J.Mielby,F.H.Richter,G.H.Wang,G.Prieto,T.Kasama,C.Weidenthaler,H.J.Bongard,S.Kegn?s,A.Furstner,F.Schuth,Angew.Chem.Int.Ed.,2014,53,8645-8648.
[19]E.Rangel Rangel,E.M.Maya,F.Sánchez,J.G.de la Campa,M.Igle-sias,Green Chem.,2015,17,466-473.
[20]T.L.Cui,W.Y.Ke,W.B.Zhang,H.H.Wang,X.H.Li,J.Chen,Angew.Chem.Int.Ed.,2016,55,9178-9182.
[21]Y.Kitamura,S.Sako,T.Udzu,A.Tsutsui,T.Maegawa,Y.Monguchi,H.Sajiki,Chem.Commun.,2007,5069-5071.
[22]D.H.Lee,J.Y.Jung,M.J.Jin,Green Chem.,2010,12,2024-2029.
[23]J.W.Sun,Y.S.Fu,G.Y.He,X.Q.Sun,X.Wang,Appl.Catal.B,2015,165,661-667.
[24]R.Sun,B.Liu,B.G.Li,S.Y.Jie,ChemC atC hem,2016,8,3261-3271.
[25]C.J.Welch,J.Albaneze-Walker,W.R.Leonard,M.Biba,J.DaS ilva,D.Henderson,B.Laing,D.J.Mathre,S.Spencer,X.D.Bu,T.B.Wang,Org.Process Res.Dev.,2005,9,198-205.
[26]Z.Wang,Y.Yu,Y.X.Zhang,S.Z.Li,H.Qian,Z.Y.Lin,Green Chem.,2015,17,413-420.
[27]T.Fujihara,T.Yoshikawa,M.Satou,H.Ohta,J.Terao,Y.Tsuji,Chem.Commun.,2015,51,17382-17385.
[28]A.K.Rathi,M.B.Gawande,J.Pechousek,J.Tucek,C.Aparicio,M.Petr,O.Tomanec,R.Krikavova,Z.Travnicek,R.S.Varma,R.Zboril,Green Chem.,2016,18,2363-2373.
[29]Z.M.Dong,Z.B.Ye,Adv.Synth.Catal.,2014,356,3401-3414.
[30]A.Molnar,Chem.Rev.,2011,111,2251-2320.
[31]T.Iwai,R.Tanaka,T.Harada,M.Sawamura,Chem.Eur.J.,2014,20,1057-1065.
[32]D.Martinez-Solorio,B.Melillo,L.Sanchez,Y.Liang,E.Lam,K.N.Houk,A.B.Smith,J.Am.Chem.Soc.,2016,138,1836-1839.
[33]Y.B.Zhou,C.Y.Li,M.Li,Y.J.Ding,Z.P.Zhan,Adv.Synth.Catal.,2015,357,2503-2508.
[34]D.Sahu,A.R.Silva,P.Das,Catal.Commun.,2016,86,32-35.
[35]T.J.Hu,T.Schulz,C.Torborg,X.R.Chen,J.Wang,M.Beller,J.Huang,Chem.Commun.,2009,7330-7332.
[36]J.L.Zhang,X.R.Chen,T.J.Hu,Y.Zhang,K.L.Xu,Y.P.Yu,J.Huang,Catal.Lett.,2010,139,56-60.
[37]T.J.Hu,X.R.Chen,J.Wang,J.Huang,ChemC atC hem,2011,3,661-665.
[38]Y.P.Yu,T.J.Hu,X.R.Chen,K.L.Xu,J.L.Zhang,J.Huang,Chem.Commun.,2011,47,3592-3594.
[39]Y.Li,F.Mao,T.Chen,Z.C.Zhou,Y.Wang,J.Huang,Adv.Synth.Catal.,2015,357,2827-2832.
[40]L.F.Geng,Y.Li,Z.L.Qi,H.P.Fan,Z.C.Zhou,R.Z.Chen,Y.Wang,J.Huang,Catal.Commun.,2016,82,24-28.
[41]B.J.Gallon,R.W.Kojima,R.B.Kaner,P.L.Diaconescu,Angew.Chem.Int.Ed.,2007,46,7251-7254.
[42]B.M.Choudary,M.Roy,S.Roy,M.L.Kantam,B.Sreedhar,K.V.Kumar,Adv.Synth.Catal.,2006,348,1734-1742.
[43]S.Dutt,R.Kumar,P.F.Siril,RSC Adv.,2015,5,33786-33791.
[44]H.A.Patel,A.L.Patel,A.V.Bedekar,New J.Chem.,2016,40,8935-8945.
[45]C.A.Wheaton,J.P.J.Bow,M.Stradiotto,Organmetallics,2013,32,6148-6161.
[2]A.J.J.Lennox,G.C.Lloyd-Jones,Chem.Soc.Rev.,2014,43,412-443.
[3]J.K.Wang,Y.X.Zong,X.C.Wang,Y.L.Hu,G.R.Yue,Y.Pan,Green Chem.,2016,18,967-973.
[4]G.D.Ding,W.T.Wang,T.Jiang,B.X.Han,Green Chem.,2013,15,3396-3403.
[5]A.Molnar,Chem.Rev.,2011,111,2251-2320.
[6]J.F.Hartwig,Nature,2008,455,314-322.
[7]A.Fihri,M.Bouhrara,B.Nekoueishahraki,J.M.Basset,V.Polshet-tiwar,Chem.Soc.Rev.,2011,40,5181-5203.
[8]N.Miyaura,A.Suzuki,Chem.Rev.,1995,95,2457-2483.
[9]S.Paul,M.M.Islam,S.M.Islam,RSC Adv.,2015,5,42193-42221.
[10]P.Das,W.Linert,Coord.Chem.Rev.,2016,311,1-23.
[11]R.Garrido,P.S.Hernandez-Montes,A.Gordillo,P.Gomez-Sal,C.Lopez-Mardomingo,E.de Jesus,Organometallics,2015,34,1855-1863.
[12]Y.Nakayama,N.Yokoyama,H.Nara,T.Kobayashi,M.Fujiwhara,Adv.Synth.Catal.,2015,357,2322-2330.
[13]N.Dehury,N.Maity,S.K.Tripathy,J.M.Basset,S.Patra,ACS Catal.,2016,6,5535-5540.
[14]L.C.Lee,J.He,J.Q.Yu,C.W.Jones,ACS Catal.,2016,6,5245-5250.
[15]S.Roy,H.Plenio,Adv.Synth.Catal.,2010,352,1014-1022.
[16]W.Q.Fu,Y.Feng,Z.X.Fang,Q.Chen,T.Tang,Q.Y.Yu,T.D.Tang,Chem.Commun.,2016,52,3115-3118.
[17]J.X.Yang,X.M.Tan,Y.Wang,X.H.Wang,J.Porous Mater.,2013,20,501-506.
[18]F.Wang,J.Mielby,F.H.Richter,G.H.Wang,G.Prieto,T.Kasama,C.Weidenthaler,H.J.Bongard,S.Kegn?s,A.Furstner,F.Schuth,Angew.Chem.Int.Ed.,2014,53,8645-8648.
[19]E.Rangel Rangel,E.M.Maya,F.Sánchez,J.G.de la Campa,M.Igle-sias,Green Chem.,2015,17,466-473.
[20]T.L.Cui,W.Y.Ke,W.B.Zhang,H.H.Wang,X.H.Li,J.Chen,Angew.Chem.Int.Ed.,2016,55,9178-9182.
[21]Y.Kitamura,S.Sako,T.Udzu,A.Tsutsui,T.Maegawa,Y.Monguchi,H.Sajiki,Chem.Commun.,2007,5069-5071.
[22]D.H.Lee,J.Y.Jung,M.J.Jin,Green Chem.,2010,12,2024-2029.
[23]J.W.Sun,Y.S.Fu,G.Y.He,X.Q.Sun,X.Wang,Appl.Catal.B,2015,165,661-667.
[24]R.Sun,B.Liu,B.G.Li,S.Y.Jie,ChemC atC hem,2016,8,3261-3271.
[25]C.J.Welch,J.Albaneze-Walker,W.R.Leonard,M.Biba,J.DaS ilva,D.Henderson,B.Laing,D.J.Mathre,S.Spencer,X.D.Bu,T.B.Wang,Org.Process Res.Dev.,2005,9,198-205.
[26]Z.Wang,Y.Yu,Y.X.Zhang,S.Z.Li,H.Qian,Z.Y.Lin,Green Chem.,2015,17,413-420.
[27]T.Fujihara,T.Yoshikawa,M.Satou,H.Ohta,J.Terao,Y.Tsuji,Chem.Commun.,2015,51,17382-17385.
[28]A.K.Rathi,M.B.Gawande,J.Pechousek,J.Tucek,C.Aparicio,M.Petr,O.Tomanec,R.Krikavova,Z.Travnicek,R.S.Varma,R.Zboril,Green Chem.,2016,18,2363-2373.
[29]Z.M.Dong,Z.B.Ye,Adv.Synth.Catal.,2014,356,3401-3414.
[30]A.Molnar,Chem.Rev.,2011,111,2251-2320.
[31]T.Iwai,R.Tanaka,T.Harada,M.Sawamura,Chem.Eur.J.,2014,20,1057-1065.
[32]D.Martinez-Solorio,B.Melillo,L.Sanchez,Y.Liang,E.Lam,K.N.Houk,A.B.Smith,J.Am.Chem.Soc.,2016,138,1836-1839.
[33]Y.B.Zhou,C.Y.Li,M.Li,Y.J.Ding,Z.P.Zhan,Adv.Synth.Catal.,2015,357,2503-2508.
[34]D.Sahu,A.R.Silva,P.Das,Catal.Commun.,2016,86,32-35.
[35]T.J.Hu,T.Schulz,C.Torborg,X.R.Chen,J.Wang,M.Beller,J.Huang,Chem.Commun.,2009,7330-7332.
[36]J.L.Zhang,X.R.Chen,T.J.Hu,Y.Zhang,K.L.Xu,Y.P.Yu,J.Huang,Catal.Lett.,2010,139,56-60.
[37]T.J.Hu,X.R.Chen,J.Wang,J.Huang,ChemC atC hem,2011,3,661-665.
[38]Y.P.Yu,T.J.Hu,X.R.Chen,K.L.Xu,J.L.Zhang,J.Huang,Chem.Commun.,2011,47,3592-3594.
[39]Y.Li,F.Mao,T.Chen,Z.C.Zhou,Y.Wang,J.Huang,Adv.Synth.Catal.,2015,357,2827-2832.
[40]L.F.Geng,Y.Li,Z.L.Qi,H.P.Fan,Z.C.Zhou,R.Z.Chen,Y.Wang,J.Huang,Catal.Commun.,2016,82,24-28.
[41]B.J.Gallon,R.W.Kojima,R.B.Kaner,P.L.Diaconescu,Angew.Chem.Int.Ed.,2007,46,7251-7254.
[42]B.M.Choudary,M.Roy,S.Roy,M.L.Kantam,B.Sreedhar,K.V.Kumar,Adv.Synth.Catal.,2006,348,1734-1742.
[43]S.Dutt,R.Kumar,P.F.Siril,RSC Adv.,2015,5,33786-33791.
[44]H.A.Patel,A.L.Patel,A.V.Bedekar,New J.Chem.,2016,40,8935-8945.
[45]C.A.Wheaton,J.P.J.Bow,M.Stradiotto,Organmetallics,2013,32,6148-6161.