胺化ZPS-IPPA轴向配位固载手性Salen Mn（Ⅲ）催化剂的合成及催化烯烃的不对称环氧化反应研究
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摘要
多相手性催化是目前催化领域重要的研究方向,多相手性催化环氧化是最为活跃的研究课题之一。聚(苯乙烯基-异丙烯膦酸)-磷酸氢锆(ZPS-IPPA)是本课题组在新型催化剂载体领域开发出来的一类新型复合催化剂载体材料。在性能上表现出较高的热稳定性和较好的耐酸碱性能,在结构上具有聚苯乙烯有机链段的可设计、可修饰性及层状结构,是集有机、无机载体的优点为一体的新型载体。
本文首先对ZPS-IPPA中的苯环进行氯甲基修饰,进而进行胺化修饰,分别接枝不同链长的二胺(乙二胺、1,4-丁二胺,1,6-己二胺,对苯胺,联苯胺及4,4'-二胺基二苯醚)和多胺(二乙烯三胺、三乙烯四胺及四乙烯五胺),再利用二胺或多胺端基氮原子与均相手性Salen Mn(Ⅲ)配合物中心的Mn原子进行轴向配位固载,实现了手性均相催化剂的多相化。运用FT-IR、DRUV-Vis、AAS、XPS、N_2吸附、SEM、TEM和TG等测试技术对同载型手性Salen Mn(Ⅲ)催化剂进行了表征。分别以次氯酸钠和间氯过氧苯甲酸为氧源考察了固载手性Salen Mn(Ⅲ)催化剂催化苯乙烯、α-甲基苯乙烯及茚的不对称环氧化反应的性能。研究了助催化剂、反应时间、反应温度、轴向接枝链长及催化剂用量对烯烃环氧化反应的影响。结果表明,同载手性Salen Mn(Ⅲ)催化剂表现出与均相手性Salen Mn(Ⅲ)值相当或更高的催化活性和对映选择性,尤其在对α-甲基苯乙烯的不对称环氧化反应时,转化率达68%,ee值达99%。固载催化剂有优良的重复使用性,重复使用8次后,催化性能无明显降低。
In recent years,the heterogeneous asymmetric catalysis has received more and more attention.Among all the reactions,the heterogeneous asymmetric epoxidation is the most impressive.In this paper,Zirconium poly(styrene-isopropenyl phosphonate)-phosphate (ZPS-IPPA),was synthesized.There are many caves,channels and pores with different shapes and sizes in the ZPS-IPPA particles.This kind of organic-inorganic hybrid materials has high thermal stability,acid and base stabilities, which can be used as a new kind of support material posessing advantages of organic-inorganic supports.
In this work,it is pursued our research in the untapped area and diamine or ployamines modified ZPS-IPPA was prepared by the reaction of ZCMPS-IPPA with diamines or ployamines and then homogeneous chiral Salen Mn(Ⅲ) was immobilized onto the diamine or ployamines modified ZPS-IPPA by axial coordination thus a new type of heterogeneous chiral Salen Mn(Ⅲ) catalysts was obtained.All the heterogeneous chiral Salen Mn(Ⅲ) catalysts prepared were characterized by FT-IR, diffusion reflection UV-Vis,AAS,N_2 volumetric adsorption,SEM,TEM and TG..The NaClO and m-CPBA were used as oxidant for asymmetric epoxidation of styrene,α-methylstyrene and indene respectively.The factors,such as amount of catalyst, co-catalyst,the reaction time,the reaction temperature solvent and axial length were investigated for asymmetric epoxidation ofα-methylstyrene.The results confirmed that the catalysts exhibit comparable or even higher activity and enantioselectivity for asymmetric epoxidation of various unfunctionalized alkenes than those of homogeneous Jacobsen's catalyst. Especially,in the epoxidation of a-methylstyrene,the conversion and enantiometric excess(ee) of 68%and 99%were obtained respectively.The catalysts were easily recovered by filtration and could be reused at least eight times with little loss of activity and enantioselectivity.
本文首先对ZPS-IPPA中的苯环进行氯甲基修饰,进而进行胺化修饰,分别接枝不同链长的二胺(乙二胺、1,4-丁二胺,1,6-己二胺,对苯胺,联苯胺及4,4'-二胺基二苯醚)和多胺(二乙烯三胺、三乙烯四胺及四乙烯五胺),再利用二胺或多胺端基氮原子与均相手性Salen Mn(Ⅲ)配合物中心的Mn原子进行轴向配位固载,实现了手性均相催化剂的多相化。运用FT-IR、DRUV-Vis、AAS、XPS、N_2吸附、SEM、TEM和TG等测试技术对同载型手性Salen Mn(Ⅲ)催化剂进行了表征。分别以次氯酸钠和间氯过氧苯甲酸为氧源考察了固载手性Salen Mn(Ⅲ)催化剂催化苯乙烯、α-甲基苯乙烯及茚的不对称环氧化反应的性能。研究了助催化剂、反应时间、反应温度、轴向接枝链长及催化剂用量对烯烃环氧化反应的影响。结果表明,同载手性Salen Mn(Ⅲ)催化剂表现出与均相手性Salen Mn(Ⅲ)值相当或更高的催化活性和对映选择性,尤其在对α-甲基苯乙烯的不对称环氧化反应时,转化率达68%,ee值达99%。固载催化剂有优良的重复使用性,重复使用8次后,催化性能无明显降低。
In recent years,the heterogeneous asymmetric catalysis has received more and more attention.Among all the reactions,the heterogeneous asymmetric epoxidation is the most impressive.In this paper,Zirconium poly(styrene-isopropenyl phosphonate)-phosphate (ZPS-IPPA),was synthesized.There are many caves,channels and pores with different shapes and sizes in the ZPS-IPPA particles.This kind of organic-inorganic hybrid materials has high thermal stability,acid and base stabilities, which can be used as a new kind of support material posessing advantages of organic-inorganic supports.
In this work,it is pursued our research in the untapped area and diamine or ployamines modified ZPS-IPPA was prepared by the reaction of ZCMPS-IPPA with diamines or ployamines and then homogeneous chiral Salen Mn(Ⅲ) was immobilized onto the diamine or ployamines modified ZPS-IPPA by axial coordination thus a new type of heterogeneous chiral Salen Mn(Ⅲ) catalysts was obtained.All the heterogeneous chiral Salen Mn(Ⅲ) catalysts prepared were characterized by FT-IR, diffusion reflection UV-Vis,AAS,N_2 volumetric adsorption,SEM,TEM and TG..The NaClO and m-CPBA were used as oxidant for asymmetric epoxidation of styrene,α-methylstyrene and indene respectively.The factors,such as amount of catalyst, co-catalyst,the reaction time,the reaction temperature solvent and axial length were investigated for asymmetric epoxidation ofα-methylstyrene.The results confirmed that the catalysts exhibit comparable or even higher activity and enantioselectivity for asymmetric epoxidation of various unfunctionalized alkenes than those of homogeneous Jacobsen's catalyst. Especially,in the epoxidation of a-methylstyrene,the conversion and enantiometric excess(ee) of 68%and 99%were obtained respectively.The catalysts were easily recovered by filtration and could be reused at least eight times with little loss of activity and enantioselectivity.
引文
[15]Deng L and Jacobsen E N.A Practical,Highly Enantioselective Synthesis of the Taxol Side Chain via Asymmetric Catalysis.J.Org.Chem.,1992,57(15):4320-23.
[16]Chang S,Lee N H and Jacobsen E N.Regio- and Enantioselective Catalytic Epoxidation of Conjugated Polyenes.Formal Synthesis of LTAd Methyl Ester.J.Org.Chem.,1993,58(25):6939-6941.
[17]Chang S.Galvin J M and Jacobsen E N.Effect of Chiral Quaternary Ammonium Salts on(salen)Mn-Catalyzed Epoxidation of cis-Olefins.A Highly Enantioselective,Catalytic Route to Ti0ayls-Epoxide.J.Am.Chem.Soc.1994 116(15):6937-6938
[18]Jacobsen E.N.;Deng L.;Furukawa Y.;et al.,Enantioselective catalytic epoxidation of cinnamate esters.Tetrahedron.1994,50(15),4323-4334.
[19]Blaser H.U.;Pugin B.,Chiral Reactions in Heterogeneous catalysis,ed.G Jannes and V Dubois,Plenum Press,New York,1995,p.33.
[20]Srinivasan K.;Michaud P.;Kochi J.K.,Epoxidation of Olefins with Cationic(salen)Mn~Ⅲomplexes.The Modulation of Catalytic Activity by Substituents.J.Am.Chem.Soc.1986,108(9),2309-2320.
[21]Canali L.;Cowan E.;Deleuze H.;Gibson C.L.;Sherrington D.C.,Remarkable matrix effect in polymer-supported Jacobsen's alkene epoxidation catalysts.Chem.Commun.1998,2561-2562.
[22]Fraile,J.M.;Garcia J.I.;Massam J.;Mayoral J.A.,Clay-supported non chiral and chiral Mn(salen) complexes as catalysts for olefin epoxidation.J.Mol.Catal.A 1998,136,47-53
[23]Kureshy,R.I.;Khan,N.H.;Abdi,S.H.R.;Ahmad,I.;Singh,S.;Jasra,R.V.Catal.Lett.2003,91,207.
[24]Kureshy R.I.,Khan N.H.,Abdi S.H.R.,Ahmad I.,Singh S.,Jasra R.V.,Dicationic chiral Mn(Ⅲ) salen complex exchanged in the inter-layers of montmorillonite clay:A heterogeneous enantioselective catalysts for epoxidation of nonfunctionalised alkenes.J.Catal.,221(2004)234-240.
[25]Zhang,H.;Zhang,Y.;Li,C.,Asymmetric epoxidation of unfunctional olefins catalyzed by Mn(salen) axially immobilized onto insoluble polymers.Tetrahedron:Asymmetry,16(2005)2417-2423
[26]Piaggio,P.;McMorn,P.;Langham,C.;Bethell,D.;Bulman-Page,P.C.;Hancock,F.E.;Hutchings,G.J.Asymmetric epoxidation of stilbene by manganese(Ⅲ) chiral salen complex immobilised in Al-MCM-41,New J.Chem.1998,1167-1169.
[27]Piaggio,P.;Langham,C.;McMorn,P.;Bethell,D.;Bulman-Page,P.C.;Hancock,F.E.;Sly,C.;Hutchings,G.J.Catalytic asymmetric epoxidation of stilbene using a chiral salen complex immobilized in Mn-exchanged Al-MCM-41,J.Chem.Soc.,Perkin Trans.2 2000,143-148.
[28]Piaggio,P.;McMorn,P.;Murphy,D.;Bethell,D.;Bulman-Page,P.C.;Hancock,F.E.;Sly,C.;Kerton,O.J.;Hutchings,G.J.Enantioselective epoxidation of(Z)-stilbene using a chiral Mn(Ⅲ)-salen complex:Effect of immobilization on MCM-41 on product selectivity,J.Chem.Soc.,Perkin Trans.2 2000,2008-2015.
[29]Kim,G.J.;Kim,S.H.Immobilization of new Mn(salen) complex over MCM-41 and its activity in asymmetric epoxidation of styrene.Catal.Lett.1999,57,139-143.
[30]Kim,G.J.;Shin,J.H.Application of new unsymmetrical chiral Mn(Ⅲ),Co(Ⅱ,Ⅲ) and Ti(Ⅳ)salen complexes in enantioselective catalytic reactions.Catal.Lett.1999,63,83-90.
[31]Xiang,S.;Zhang,Y,Xin,Q.;Li,C.Enantioselective epoxidation of olefins catalyzed by Mn(salen)/MCM-41 synthesized with a new anchoring method.Chem.Commun.2002.2696-2697
[32]Zhang,H.;Xiang,S.;Li,C.Enantioselective epoxidation of unfunctionalised olefins catalyzed by Mn(salen) complexes immobilized in porous materials via phenyl sulfonic group.Chem.Commun.2005,9,1209-1211.
[33]Zhang,H.;Xiang,S.;Xiao,J.;Li,C.Heterogeneous enantioselective epoxidation catalyzed by Mn(salen) complexes grafted onto mesoporous materials by phenoxy group.J.Mol.Catal.A 2005,238,175-184.
[34]Zhang,H.;Li,C.Asymmetric epoxidation of 6-cyano-2,2-dimethylchromene on Mn(salen)catalyst immobilized in mesoporous materials.Tetrahedron 2006,62,6640-6649
[35]Zhang,H.;Zhang,Y.;Li,C.Enantioselective epoxidation of unfunctionalized olefins catalyzed by the Mn(salen) catalysts immobilized in the nanopores of mesoporous materials.J.Catal.2006,238,369-381.
[36]Domi'nguez,I.;Forne's,V.;Sabater,M.J.Chiral manganese(Ⅲ) salen catalysts immobilized on MCM-41 and delaminated zeolites ITQ-2 and ITQ-6 through new axial coordinating linkers.J.Carol.2004,228,92-99.
[37]Bhattacharjee,S.;Anderson,J.A.Synthesis and characterization of novel chiral sulfonato-salen-manganese(Ⅲ) complex in a zinc-aluminium LDH host.Chem.Commun.2004,554-555.
[38]Bhattacharjee,S.;Anderson,J.A.Epoxidation by layered double hydroxide-hosted catalysts.Catalyst synthesis and use in the epoxidation of R-(+)-limonene and(-)-alpha-pinene using molecular oxygen.Catal.Lett.2004,95,119-125.
[39]Bhattacharjee,S.;Dines,T.J.;Anderson,J.A.Synthesis and application of layered double hydroxide-hosted catalysts for stereoselective epoxidation using molecular oxygen or air.J.Catal.2004,225,398-407 Catal.A:Chemical 113(1996) 283-292
[52]Mac Leod.T.C.O.;Guedes,D.F.C.;Lelo,M.R.;Rocha,R.A.;Caetano,B.L.;Ciuffi,K.J.:Assis,M.D.Catalytic activity of Jacobsen catalyst encapsulated in an alumina matrix by the sol-gel process.J.Mol.Catal.A 2006,259,319-327.
[53]Ogunwumi,S.B.;Bein,T.Intrazeolite assembly of a chiral manganese salen epoxidation catalyst.Chem.Commun.1997,901-902.
[54]Heinrichs,C.;Ho"lderich,W.F.Novel zeolitic hosts for "ship-in-a-bottle" catalysts.Catal.Lett.1999,58,75-80.
[55]Gbery,G.;Zsigmond,A.,Jr Enantioselective epoxidations catalyzed by zeolite MCM-22encapsulated Jacobsen's catalyst.Catal.Lett.2001,74,77-80.
[56]Clearfield A.,Role of ion exchange in solid-state chemistry.Chem.Rev.1988,88(1),125-148.
[57]蒋文伟,童长春.固体酸SO_4~(2-)/TiO_(2-)Al_2O_3的合成及酯化活性考察,成都科技大学学报,1999,3:50
[58]马学兵,傅相锴,李龙芹等.一些晶态层状有机无机混合磷酸锆的制备表征和层间距分析.无机化学学报,2001,1:124
[59]傅相锴,何佑秋,马学兵等.带络合基团的混合磷酸膦酸锆载体的研制.催化学报.1996,17(3)260
[60]肖进兵,徐金锁,唐颐等:层状苯膦酸磷酸锆的合成与磺化研究.高等学校化学学报.1998,7:1107
[61]傅相锴,罗必奎,雷庆英;磺化苯膦酸锆催化反应研究.[J].应用化学,1991,8(5):6-8
[62]傅相锴,温淑英等;二丁胺甲基膦酸锆的苄基季铵化物及其相转移催化作用.[J].应用化学,1995,12(2):20
[63]傅相锴,马学兵等;羧甲基胺-N,N-双甲撑基二膦酸锆-钯催化剂的催化加氢性能研究.应用化学,1997,14(1):74-76
[64]马学兵,傅相锴.(N-膦酸亚甲基)亚氨基二乙酸-亚磷酸氢锆-钯催化剂的催化加氢活性;离子交换与吸附,1998,14(1):11-17
[65]傅相锴,马学兵等;亚磷酸氢锆-聚乙烯吡咯烷酮-钯催化剂的催化加氢性能.应用化学,1998,15(1):17-21
[66]罗中杰,马学兵,龚成斌,傅相锴;胍乙基、双氰乙基胺乙基及胺乙基膦酸锆-钯催化剂的催化加氢性能.应用化学.1999,16(1):11-14
[67]龚成斌,马学兵,傅相锴;含膦氮配体的混合膦酸锆-钯催化剂的研制.分子催化.1999,13(5):327-329
[68]Ma X B,Fu X K.Synthesis of a new type of amphilic and water-soluble tertiary phosphine ligands substituted by an ethoxylated phosphonic acid chain and their palladium complexes.J. Mol Catalysis A:Chemical:2003,195:47-53
[69]Ma X B,Fu X K.Synthesis of the novel layered amorphous and crystalline zirconium phosphate-phosphonatesZr(HPO_4)[O_3PCH_2N(CH_2CH_2)_2O]·nH_2O,Zr(HPO_4)[O_3PCH_2N(CH_2CO _2H)_2]·nH_2O,zirconium phosphonates Zr[(O_3PCH_2)NCH_2CO_2H]·nH_2O and the catalytic activities of their palladium complexes in hydrogenation.J.of Mol Catalysis A:Chemical:2004,208:129-133
[70]Zeng R Q,Fu X K,Gong C B,Sui Y,et al.Preparation and catalytic property of the solid base supported on the mixed zirconium phosphate phosphonate for Knoevenagel condensation.J.Mol Catalysis A:Chemical:2005,229:1-5
[71]Sui Y,Xiang Kai Fu,Ma X B.Study of preparation and reaction mechanism of new types of phosphonous acid-terminated oligostyrene.Reactive & Functional Polymers,2005,64:55-62.
[72]傅相锴,邹旷东,富丹,龚永锋;苯乙烯-异丙烯基膦酸共聚物,中国发明专利,申请号:200610095053.1
[73]邹旷东,傅相锴,龚永锋,曾仁权,富丹;新型催化载体材料ZPS-IPPA的合成与表征,功能材料,2007,38:1152-1155
[74]Gong B W,Fu X K,Chen J X,Li Y D,Zou X C,Tu X B,Ding P P,Ma L P.Synthesis of a new type of immobilized chiral salen Mn(Ⅲ) complex as effective catalysts for asymmetric epoxidation of unfunctionalized olefins.Journal of Catalysis,2009,262,9-17
[75]Sui Y,Fu Xiang-Kai,Ma X B,Zeng R Q.Preparation,characterization and application of a new type of ion exchanger and solid acid zirconium sulfonated oligo-polystyrenylphosphonate-phosphate supported on ZrO_2[J].J.Mol Catalysis A:Chemical,2004,217:133-138.
[76]Sui Y,Fu Xiang-Kai,Chen J R,Ma X B,Zeng R Q.Preparation and properties of solid acid zirconium oligo(sulfostyrenyl)phosphonate hydrogen phosphate supported on TiO_2[J].Materials Letters,2005,59:2115-2119.
[77]傅相锴,隋岩,富丹等;氯甲基醚合成氯甲基化低聚苯乙烯基膦酸.磷酸盐;中国发明专利,申请号:200510057167.2
[78]傅相锴,隋岩;ZrSPP-ZP固载多甘醇、多胺/Mo配合物催化烯烃环氧化反应(大会主题报告);中国化学会第九届全国络合催化学术讨论会(2005,10,17-19 郑州);会议论文集.p21
[79]傅相锴,隋岩;THAM衍生席夫碱双氧Mo(Ⅵ)配合物催化环己烯环氧化反应;中国化学会第九届全国络合催化学术讨论会(2005,10,17-19 郑州);会议论文集,233-234
[80]马学兵,周锡兰,傅相锴;光学活性1,1'-联萘-2,2'-二酚的固载;中国化学会第九届全国络合催化学术讨论会(2005,10,17-19 郑州);会议论文集,P231
[81]Botao Zheng,Xinjun Wu,Xiangkai Fu,Xuebing Ma,Lingshan Xiao,Yeling Ji.Zirconium phosphonate immobilized chiral amino alcohol for heterogeneous enantioselective addition of diethylzinc to benzaldehyde.Catalysis Communications.2007;8:1923-1928.
[82]Xinjun Wu,Xuebing Ma,Xiangkai Fu,Yeling Ji,Qiang Wang,Xiao Jia.Synthesis and characterization of a novel type of self-assembled chiral zirconium phosphonates and its application for heterogeneous asymmetric catalysis.J.Mol.Catal,A.2007;265:316-322.
[83]Bai RF,FU XK,Bao HB,Ren WS.Chiral Salen Mn(Ⅲ) complex axial coordination immobilized on diamine modified ZSPP and their catalytic epoxidation of styrene.Catalysis Communication.2008;9:1588-1594.
[84]包河彬,傅相锴,白若飞,任文山,涂小波.新固载型手性Salen Mn(Ⅲ)催化剂的合成及催化苯乙烯不对称环氧化反应.高等学校化学学报,2008,29(5):927-931
[85]Ren W.S.;Fu X.K.;Bao H.B.;Bai R.F.;Ding P.P.;Sui B.L..Enantioselective epoxidation of unfunctionalized olefins catalyzed by chiral salen Mn(Ⅲ) catalyst immobilized on zirconium oligostyrenylphosphonate-phosphate.Catalysis Communication 2009;10:788-793.
[86]Shen H.S.,Fu X.K.,Bao H.B.,Chen J.X.,Gong B.W.,Synthesis and characterization of a new kind of immobilized Mn(salen) and catalytic epoxidation of styrene on the catalyst.Polym.Adv.Technol.20(2009) 77-83.
[87]Merrifield R.B.Solid Phase Peptide Synthesis Ⅰ.The Synthesis of a Tetrapeptide.J.Am.Chem.Soc.,1963,85,2149-2154.
[88]Gil S.,Gonzalez R.,Mestres R.,Sanz V.,Zapater A.Alkene epoxidations catalysed by Mo(Ⅵ)supported on Merrifield's polymer,React.Funct.Polym.,1999,42,65-72.
[89]Asefa T.,Maclachlan M.J.,Coombs N.,Ozin G.A.Periodic mesoporous organosilicas with organic groups inside the channel walls.Nature,1999,402,867-871.
[90]Inagaki S.,Guan S.,Fukushima Y.,Ohsuna T.,Terasaki O.Novel mesoporous materials with a uniform distribution of organic groups and inorganic oxide in their frameworks.J.Am.Chem.Soc.,1999,121,9611-9614.
[91]Corriu R.J.P.,Leclercq D.Recent developments of molecular chemistry for sol-gel processes.Angew Chem.Int.Ed.,1996,35,1420-1436.
[92]Boury B.,Corriu R.J.P.,Strat V.Le,Delord P.,Nobili M.Nanostructured Silica-Based Organic-Inorganic Hybrid Materials - Evidence for Self-Organization of a Xerogel Prepared by Sol-Gel Polymerization.Angew Chem.Int.Ed.,1999,38,3172-3175.
[93]Stein A.,Melde B.J.,Schroden R.C.Hybrid Inorganic±Organic Mesoporous SilicatesDNanoscopic Reactors Coming of Age.Adv Mater.,2000,12,1403-1419.
[94]赵彦生,李万捷,温亚龙,李居英.异屏息膦酸的合成及表征,太原工业大学学报,1996,27,11-14.
[95]Jacobsen E N,Zhang W,Muci AR,Ecker J R and Deng L.Highly Enantioselective Epoxidation Catalysts Derived from 1,2-Diaminocyclohexane.J.Am.Chem.Soc.,1991,113:7063-7066.
[96]Brandes B D and Jacobsen E N.Enantioselective catalytic epoxidaiton of tetrasubstituted olefins.Tetrahedron Lett.,1995,36(29):5123-5126.
[97]Silva A.R.,Figueiredo J.L.,Freire C.,Castro B.D.,Castro B.D.Manganese(Ⅲ) salen complexes anchored onto activated carbon as heterogeneous catalysts for the epoxidation of olefins.Microporous Mesoporous Mater,2004,68:83-89.
[98]Tong J.H.,Zhang R.,Li Z.,Xia C.G.Highly effective catalysts of natural polymer supported Salophen Mn(Ⅲ) complexes for aerobic oxidation of cyclohexene.J Mol Catal A:Chem[J],2006,249:47-52
[99]Yu K.,Lou L.L.,Lai C.,Wang S.J.,Ding F.,Liu S.X.Asymmetric epoxidation of unfunctionalized olefins catalyzed by Mn(Ⅲ) salen complex immobilized on MCM-48.Catal.Commun.,2006,7,1057.
[100]Feichtinger D.;Plattner D.A.;Direct proof for O=Mn(Ⅴ)(Salen) complexs.Angew.Chem.Int.Ed.1997,36,1718 - 1719.
[101]Finney N.S.;Pospisil P.J.;Chang S.;Palucki M.;Konsler R.G.;Hansen K.B.;Jacobsen E.N.,On the vibility of oxametallacyclic intermediates in the(salen)Mn-catalyzed asymmetric epoxidation.Angew.Chem.Int.Ed.1997,36 1720 - 1723.
[102]Linde C.;Arnold M.;Norrby P.O.;Akermark B.,Is there a radical intermediate in the(salen)Mn-catalyzed epoxidation of alkene.Angew.Chem.Int.Ed.1997,36 1723 - 1725.
[103]Srinivasan,P.;Michaud,P.;Kochi,J.K.,Epoxidation of olefins with cationic (salen)manganese(Ⅲ) complexes.The modulation of catalytic activity by substituents.J.Am.Chem.Soc.1986,108,2309-2320.
[104]Cavallo L.;Jacobsen H.,Radical Intermediates in the Jacobsen ± Katsuki Epoxidation Angew.Chem.Int.Ed.2000,39,3589-3592.
[105]Bahraoui J.E.;Wiest O.;Feichtinger D.,Dietmar A.Plattner Rate Enhancement and Enantioselectivity of the Jacobsen ± Katsuki Epoxidation:The Significance of the Sixth Coordination Site.Angew.Chem.Int.Ed.2001,40,11,2073-2076.
[106]Scheurer A.;Maid H.;Hampel F.;et al.,Influence of the Conformation of Salen Complexes on the Stereochemistry of the Asymmetric Epoxidation of Olefins.Eur.J.Org.Chem.2005,2566-2574.
[107]Linde C.;Koliai N.;Norrby P.O.,Experimental Evidence for Multiple Oxidation Pathways in the(salen)Mn-Catalyzed Epoxidation of Alkenes.Chem-A Eur.J.2002,8(11),2568-2573
[108]Linker T.,The Jacobsen-Katsuki Epoxidation and Its Controversial Mechanism.Angew.Chem.Int.Ed.1997,36(19),2060-2062.
[109]Jacobsen H.;Cavallo L.,A Possible Mechanism for Enantioselectivity in the Chiral Epoxidation of Olefins with[Mn(salen)]Catalysts.Chem.Eur.J.2001,7(4),800-807.
[110]Cavallo L.;Jacobsen H.,Electronic Effects in(salen)Mn-Based Epoxidation Catalysts.J Org.Chem.2003,68,6202-6207.
[16]Chang S,Lee N H and Jacobsen E N.Regio- and Enantioselective Catalytic Epoxidation of Conjugated Polyenes.Formal Synthesis of LTAd Methyl Ester.J.Org.Chem.,1993,58(25):6939-6941.
[17]Chang S.Galvin J M and Jacobsen E N.Effect of Chiral Quaternary Ammonium Salts on(salen)Mn-Catalyzed Epoxidation of cis-Olefins.A Highly Enantioselective,Catalytic Route to Ti0ayls-Epoxide.J.Am.Chem.Soc.1994 116(15):6937-6938
[18]Jacobsen E.N.;Deng L.;Furukawa Y.;et al.,Enantioselective catalytic epoxidation of cinnamate esters.Tetrahedron.1994,50(15),4323-4334.
[19]Blaser H.U.;Pugin B.,Chiral Reactions in Heterogeneous catalysis,ed.G Jannes and V Dubois,Plenum Press,New York,1995,p.33.
[20]Srinivasan K.;Michaud P.;Kochi J.K.,Epoxidation of Olefins with Cationic(salen)Mn~Ⅲomplexes.The Modulation of Catalytic Activity by Substituents.J.Am.Chem.Soc.1986,108(9),2309-2320.
[21]Canali L.;Cowan E.;Deleuze H.;Gibson C.L.;Sherrington D.C.,Remarkable matrix effect in polymer-supported Jacobsen's alkene epoxidation catalysts.Chem.Commun.1998,2561-2562.
[22]Fraile,J.M.;Garcia J.I.;Massam J.;Mayoral J.A.,Clay-supported non chiral and chiral Mn(salen) complexes as catalysts for olefin epoxidation.J.Mol.Catal.A 1998,136,47-53
[23]Kureshy,R.I.;Khan,N.H.;Abdi,S.H.R.;Ahmad,I.;Singh,S.;Jasra,R.V.Catal.Lett.2003,91,207.
[24]Kureshy R.I.,Khan N.H.,Abdi S.H.R.,Ahmad I.,Singh S.,Jasra R.V.,Dicationic chiral Mn(Ⅲ) salen complex exchanged in the inter-layers of montmorillonite clay:A heterogeneous enantioselective catalysts for epoxidation of nonfunctionalised alkenes.J.Catal.,221(2004)234-240.
[25]Zhang,H.;Zhang,Y.;Li,C.,Asymmetric epoxidation of unfunctional olefins catalyzed by Mn(salen) axially immobilized onto insoluble polymers.Tetrahedron:Asymmetry,16(2005)2417-2423
[26]Piaggio,P.;McMorn,P.;Langham,C.;Bethell,D.;Bulman-Page,P.C.;Hancock,F.E.;Hutchings,G.J.Asymmetric epoxidation of stilbene by manganese(Ⅲ) chiral salen complex immobilised in Al-MCM-41,New J.Chem.1998,1167-1169.
[27]Piaggio,P.;Langham,C.;McMorn,P.;Bethell,D.;Bulman-Page,P.C.;Hancock,F.E.;Sly,C.;Hutchings,G.J.Catalytic asymmetric epoxidation of stilbene using a chiral salen complex immobilized in Mn-exchanged Al-MCM-41,J.Chem.Soc.,Perkin Trans.2 2000,143-148.
[28]Piaggio,P.;McMorn,P.;Murphy,D.;Bethell,D.;Bulman-Page,P.C.;Hancock,F.E.;Sly,C.;Kerton,O.J.;Hutchings,G.J.Enantioselective epoxidation of(Z)-stilbene using a chiral Mn(Ⅲ)-salen complex:Effect of immobilization on MCM-41 on product selectivity,J.Chem.Soc.,Perkin Trans.2 2000,2008-2015.
[29]Kim,G.J.;Kim,S.H.Immobilization of new Mn(salen) complex over MCM-41 and its activity in asymmetric epoxidation of styrene.Catal.Lett.1999,57,139-143.
[30]Kim,G.J.;Shin,J.H.Application of new unsymmetrical chiral Mn(Ⅲ),Co(Ⅱ,Ⅲ) and Ti(Ⅳ)salen complexes in enantioselective catalytic reactions.Catal.Lett.1999,63,83-90.
[31]Xiang,S.;Zhang,Y,Xin,Q.;Li,C.Enantioselective epoxidation of olefins catalyzed by Mn(salen)/MCM-41 synthesized with a new anchoring method.Chem.Commun.2002.2696-2697
[32]Zhang,H.;Xiang,S.;Li,C.Enantioselective epoxidation of unfunctionalised olefins catalyzed by Mn(salen) complexes immobilized in porous materials via phenyl sulfonic group.Chem.Commun.2005,9,1209-1211.
[33]Zhang,H.;Xiang,S.;Xiao,J.;Li,C.Heterogeneous enantioselective epoxidation catalyzed by Mn(salen) complexes grafted onto mesoporous materials by phenoxy group.J.Mol.Catal.A 2005,238,175-184.
[34]Zhang,H.;Li,C.Asymmetric epoxidation of 6-cyano-2,2-dimethylchromene on Mn(salen)catalyst immobilized in mesoporous materials.Tetrahedron 2006,62,6640-6649
[35]Zhang,H.;Zhang,Y.;Li,C.Enantioselective epoxidation of unfunctionalized olefins catalyzed by the Mn(salen) catalysts immobilized in the nanopores of mesoporous materials.J.Catal.2006,238,369-381.
[36]Domi'nguez,I.;Forne's,V.;Sabater,M.J.Chiral manganese(Ⅲ) salen catalysts immobilized on MCM-41 and delaminated zeolites ITQ-2 and ITQ-6 through new axial coordinating linkers.J.Carol.2004,228,92-99.
[37]Bhattacharjee,S.;Anderson,J.A.Synthesis and characterization of novel chiral sulfonato-salen-manganese(Ⅲ) complex in a zinc-aluminium LDH host.Chem.Commun.2004,554-555.
[38]Bhattacharjee,S.;Anderson,J.A.Epoxidation by layered double hydroxide-hosted catalysts.Catalyst synthesis and use in the epoxidation of R-(+)-limonene and(-)-alpha-pinene using molecular oxygen.Catal.Lett.2004,95,119-125.
[39]Bhattacharjee,S.;Dines,T.J.;Anderson,J.A.Synthesis and application of layered double hydroxide-hosted catalysts for stereoselective epoxidation using molecular oxygen or air.J.Catal.2004,225,398-407 Catal.A:Chemical 113(1996) 283-292
[52]Mac Leod.T.C.O.;Guedes,D.F.C.;Lelo,M.R.;Rocha,R.A.;Caetano,B.L.;Ciuffi,K.J.:Assis,M.D.Catalytic activity of Jacobsen catalyst encapsulated in an alumina matrix by the sol-gel process.J.Mol.Catal.A 2006,259,319-327.
[53]Ogunwumi,S.B.;Bein,T.Intrazeolite assembly of a chiral manganese salen epoxidation catalyst.Chem.Commun.1997,901-902.
[54]Heinrichs,C.;Ho"lderich,W.F.Novel zeolitic hosts for "ship-in-a-bottle" catalysts.Catal.Lett.1999,58,75-80.
[55]Gbery,G.;Zsigmond,A.,Jr Enantioselective epoxidations catalyzed by zeolite MCM-22encapsulated Jacobsen's catalyst.Catal.Lett.2001,74,77-80.
[56]Clearfield A.,Role of ion exchange in solid-state chemistry.Chem.Rev.1988,88(1),125-148.
[57]蒋文伟,童长春.固体酸SO_4~(2-)/TiO_(2-)Al_2O_3的合成及酯化活性考察,成都科技大学学报,1999,3:50
[58]马学兵,傅相锴,李龙芹等.一些晶态层状有机无机混合磷酸锆的制备表征和层间距分析.无机化学学报,2001,1:124
[59]傅相锴,何佑秋,马学兵等.带络合基团的混合磷酸膦酸锆载体的研制.催化学报.1996,17(3)260
[60]肖进兵,徐金锁,唐颐等:层状苯膦酸磷酸锆的合成与磺化研究.高等学校化学学报.1998,7:1107
[61]傅相锴,罗必奎,雷庆英;磺化苯膦酸锆催化反应研究.[J].应用化学,1991,8(5):6-8
[62]傅相锴,温淑英等;二丁胺甲基膦酸锆的苄基季铵化物及其相转移催化作用.[J].应用化学,1995,12(2):20
[63]傅相锴,马学兵等;羧甲基胺-N,N-双甲撑基二膦酸锆-钯催化剂的催化加氢性能研究.应用化学,1997,14(1):74-76
[64]马学兵,傅相锴.(N-膦酸亚甲基)亚氨基二乙酸-亚磷酸氢锆-钯催化剂的催化加氢活性;离子交换与吸附,1998,14(1):11-17
[65]傅相锴,马学兵等;亚磷酸氢锆-聚乙烯吡咯烷酮-钯催化剂的催化加氢性能.应用化学,1998,15(1):17-21
[66]罗中杰,马学兵,龚成斌,傅相锴;胍乙基、双氰乙基胺乙基及胺乙基膦酸锆-钯催化剂的催化加氢性能.应用化学.1999,16(1):11-14
[67]龚成斌,马学兵,傅相锴;含膦氮配体的混合膦酸锆-钯催化剂的研制.分子催化.1999,13(5):327-329
[68]Ma X B,Fu X K.Synthesis of a new type of amphilic and water-soluble tertiary phosphine ligands substituted by an ethoxylated phosphonic acid chain and their palladium complexes.J. Mol Catalysis A:Chemical:2003,195:47-53
[69]Ma X B,Fu X K.Synthesis of the novel layered amorphous and crystalline zirconium phosphate-phosphonatesZr(HPO_4)[O_3PCH_2N(CH_2CH_2)_2O]·nH_2O,Zr(HPO_4)[O_3PCH_2N(CH_2CO _2H)_2]·nH_2O,zirconium phosphonates Zr[(O_3PCH_2)NCH_2CO_2H]·nH_2O and the catalytic activities of their palladium complexes in hydrogenation.J.of Mol Catalysis A:Chemical:2004,208:129-133
[70]Zeng R Q,Fu X K,Gong C B,Sui Y,et al.Preparation and catalytic property of the solid base supported on the mixed zirconium phosphate phosphonate for Knoevenagel condensation.J.Mol Catalysis A:Chemical:2005,229:1-5
[71]Sui Y,Xiang Kai Fu,Ma X B.Study of preparation and reaction mechanism of new types of phosphonous acid-terminated oligostyrene.Reactive & Functional Polymers,2005,64:55-62.
[72]傅相锴,邹旷东,富丹,龚永锋;苯乙烯-异丙烯基膦酸共聚物,中国发明专利,申请号:200610095053.1
[73]邹旷东,傅相锴,龚永锋,曾仁权,富丹;新型催化载体材料ZPS-IPPA的合成与表征,功能材料,2007,38:1152-1155
[74]Gong B W,Fu X K,Chen J X,Li Y D,Zou X C,Tu X B,Ding P P,Ma L P.Synthesis of a new type of immobilized chiral salen Mn(Ⅲ) complex as effective catalysts for asymmetric epoxidation of unfunctionalized olefins.Journal of Catalysis,2009,262,9-17
[75]Sui Y,Fu Xiang-Kai,Ma X B,Zeng R Q.Preparation,characterization and application of a new type of ion exchanger and solid acid zirconium sulfonated oligo-polystyrenylphosphonate-phosphate supported on ZrO_2[J].J.Mol Catalysis A:Chemical,2004,217:133-138.
[76]Sui Y,Fu Xiang-Kai,Chen J R,Ma X B,Zeng R Q.Preparation and properties of solid acid zirconium oligo(sulfostyrenyl)phosphonate hydrogen phosphate supported on TiO_2[J].Materials Letters,2005,59:2115-2119.
[77]傅相锴,隋岩,富丹等;氯甲基醚合成氯甲基化低聚苯乙烯基膦酸.磷酸盐;中国发明专利,申请号:200510057167.2
[78]傅相锴,隋岩;ZrSPP-ZP固载多甘醇、多胺/Mo配合物催化烯烃环氧化反应(大会主题报告);中国化学会第九届全国络合催化学术讨论会(2005,10,17-19 郑州);会议论文集.p21
[79]傅相锴,隋岩;THAM衍生席夫碱双氧Mo(Ⅵ)配合物催化环己烯环氧化反应;中国化学会第九届全国络合催化学术讨论会(2005,10,17-19 郑州);会议论文集,233-234
[80]马学兵,周锡兰,傅相锴;光学活性1,1'-联萘-2,2'-二酚的固载;中国化学会第九届全国络合催化学术讨论会(2005,10,17-19 郑州);会议论文集,P231
[81]Botao Zheng,Xinjun Wu,Xiangkai Fu,Xuebing Ma,Lingshan Xiao,Yeling Ji.Zirconium phosphonate immobilized chiral amino alcohol for heterogeneous enantioselective addition of diethylzinc to benzaldehyde.Catalysis Communications.2007;8:1923-1928.
[82]Xinjun Wu,Xuebing Ma,Xiangkai Fu,Yeling Ji,Qiang Wang,Xiao Jia.Synthesis and characterization of a novel type of self-assembled chiral zirconium phosphonates and its application for heterogeneous asymmetric catalysis.J.Mol.Catal,A.2007;265:316-322.
[83]Bai RF,FU XK,Bao HB,Ren WS.Chiral Salen Mn(Ⅲ) complex axial coordination immobilized on diamine modified ZSPP and their catalytic epoxidation of styrene.Catalysis Communication.2008;9:1588-1594.
[84]包河彬,傅相锴,白若飞,任文山,涂小波.新固载型手性Salen Mn(Ⅲ)催化剂的合成及催化苯乙烯不对称环氧化反应.高等学校化学学报,2008,29(5):927-931
[85]Ren W.S.;Fu X.K.;Bao H.B.;Bai R.F.;Ding P.P.;Sui B.L..Enantioselective epoxidation of unfunctionalized olefins catalyzed by chiral salen Mn(Ⅲ) catalyst immobilized on zirconium oligostyrenylphosphonate-phosphate.Catalysis Communication 2009;10:788-793.
[86]Shen H.S.,Fu X.K.,Bao H.B.,Chen J.X.,Gong B.W.,Synthesis and characterization of a new kind of immobilized Mn(salen) and catalytic epoxidation of styrene on the catalyst.Polym.Adv.Technol.20(2009) 77-83.
[87]Merrifield R.B.Solid Phase Peptide Synthesis Ⅰ.The Synthesis of a Tetrapeptide.J.Am.Chem.Soc.,1963,85,2149-2154.
[88]Gil S.,Gonzalez R.,Mestres R.,Sanz V.,Zapater A.Alkene epoxidations catalysed by Mo(Ⅵ)supported on Merrifield's polymer,React.Funct.Polym.,1999,42,65-72.
[89]Asefa T.,Maclachlan M.J.,Coombs N.,Ozin G.A.Periodic mesoporous organosilicas with organic groups inside the channel walls.Nature,1999,402,867-871.
[90]Inagaki S.,Guan S.,Fukushima Y.,Ohsuna T.,Terasaki O.Novel mesoporous materials with a uniform distribution of organic groups and inorganic oxide in their frameworks.J.Am.Chem.Soc.,1999,121,9611-9614.
[91]Corriu R.J.P.,Leclercq D.Recent developments of molecular chemistry for sol-gel processes.Angew Chem.Int.Ed.,1996,35,1420-1436.
[92]Boury B.,Corriu R.J.P.,Strat V.Le,Delord P.,Nobili M.Nanostructured Silica-Based Organic-Inorganic Hybrid Materials - Evidence for Self-Organization of a Xerogel Prepared by Sol-Gel Polymerization.Angew Chem.Int.Ed.,1999,38,3172-3175.
[93]Stein A.,Melde B.J.,Schroden R.C.Hybrid Inorganic±Organic Mesoporous SilicatesDNanoscopic Reactors Coming of Age.Adv Mater.,2000,12,1403-1419.
[94]赵彦生,李万捷,温亚龙,李居英.异屏息膦酸的合成及表征,太原工业大学学报,1996,27,11-14.
[95]Jacobsen E N,Zhang W,Muci AR,Ecker J R and Deng L.Highly Enantioselective Epoxidation Catalysts Derived from 1,2-Diaminocyclohexane.J.Am.Chem.Soc.,1991,113:7063-7066.
[96]Brandes B D and Jacobsen E N.Enantioselective catalytic epoxidaiton of tetrasubstituted olefins.Tetrahedron Lett.,1995,36(29):5123-5126.
[97]Silva A.R.,Figueiredo J.L.,Freire C.,Castro B.D.,Castro B.D.Manganese(Ⅲ) salen complexes anchored onto activated carbon as heterogeneous catalysts for the epoxidation of olefins.Microporous Mesoporous Mater,2004,68:83-89.
[98]Tong J.H.,Zhang R.,Li Z.,Xia C.G.Highly effective catalysts of natural polymer supported Salophen Mn(Ⅲ) complexes for aerobic oxidation of cyclohexene.J Mol Catal A:Chem[J],2006,249:47-52
[99]Yu K.,Lou L.L.,Lai C.,Wang S.J.,Ding F.,Liu S.X.Asymmetric epoxidation of unfunctionalized olefins catalyzed by Mn(Ⅲ) salen complex immobilized on MCM-48.Catal.Commun.,2006,7,1057.
[100]Feichtinger D.;Plattner D.A.;Direct proof for O=Mn(Ⅴ)(Salen) complexs.Angew.Chem.Int.Ed.1997,36,1718 - 1719.
[101]Finney N.S.;Pospisil P.J.;Chang S.;Palucki M.;Konsler R.G.;Hansen K.B.;Jacobsen E.N.,On the vibility of oxametallacyclic intermediates in the(salen)Mn-catalyzed asymmetric epoxidation.Angew.Chem.Int.Ed.1997,36 1720 - 1723.
[102]Linde C.;Arnold M.;Norrby P.O.;Akermark B.,Is there a radical intermediate in the(salen)Mn-catalyzed epoxidation of alkene.Angew.Chem.Int.Ed.1997,36 1723 - 1725.
[103]Srinivasan,P.;Michaud,P.;Kochi,J.K.,Epoxidation of olefins with cationic (salen)manganese(Ⅲ) complexes.The modulation of catalytic activity by substituents.J.Am.Chem.Soc.1986,108,2309-2320.
[104]Cavallo L.;Jacobsen H.,Radical Intermediates in the Jacobsen ± Katsuki Epoxidation Angew.Chem.Int.Ed.2000,39,3589-3592.
[105]Bahraoui J.E.;Wiest O.;Feichtinger D.,Dietmar A.Plattner Rate Enhancement and Enantioselectivity of the Jacobsen ± Katsuki Epoxidation:The Significance of the Sixth Coordination Site.Angew.Chem.Int.Ed.2001,40,11,2073-2076.
[106]Scheurer A.;Maid H.;Hampel F.;et al.,Influence of the Conformation of Salen Complexes on the Stereochemistry of the Asymmetric Epoxidation of Olefins.Eur.J.Org.Chem.2005,2566-2574.
[107]Linde C.;Koliai N.;Norrby P.O.,Experimental Evidence for Multiple Oxidation Pathways in the(salen)Mn-Catalyzed Epoxidation of Alkenes.Chem-A Eur.J.2002,8(11),2568-2573
[108]Linker T.,The Jacobsen-Katsuki Epoxidation and Its Controversial Mechanism.Angew.Chem.Int.Ed.1997,36(19),2060-2062.
[109]Jacobsen H.;Cavallo L.,A Possible Mechanism for Enantioselectivity in the Chiral Epoxidation of Olefins with[Mn(salen)]Catalysts.Chem.Eur.J.2001,7(4),800-807.
[110]Cavallo L.;Jacobsen H.,Electronic Effects in(salen)Mn-Based Epoxidation Catalysts.J Org.Chem.2003,68,6202-6207.