胺基功能化ZPS-PVPA固载手性Mn~Ⅲ(salen)的合成及不对称催化烯烃环氧化
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摘要
以聚(苯乙烯-苯乙烯基膦酸)-磷酸氢锆(ZPS-PVPA)为催化剂载体,通过3-氨丙基三甲氧基硅烷对其中无机磷酸氢锆的羟基进行修饰,再与均相手性Mn~Ⅲ(salen)催化剂进行轴向配位固载,实现了手性均相催化剂的非均相化.催化剂的表征结果证实制得了非均相催化剂.随后,考察了该非均相催化剂对α-甲基苯乙烯、苯乙烯以及茚不对称环氧化反应的催化性能.结果表明,以间氯过氧苯甲酸(m-CPBA)为氧化剂,在0℃反应3 h,催化剂用量为0. 03 mmol,在轴向配体N-甲基吗啉氮氧化物(NMO)的参与下,催化剂能高效催化α-甲基苯乙烯的不对称环氧化,反应的对映选择性(e. e.值)可达91. 5%,转化率为99%.此外,以茚为底物考察了催化剂的循环使用性能,结果表明,催化剂重复使用10次后,反应的e. e.值(>90%)远高于在相同条件下均相Mn~Ⅲ(salen)催化剂催化茚反应的e. e.值(65%).
Using zirconium poly( styrene-phenylvinyl-phosphonate)-phosphate( ZPS-PVPA) as a catalyst carrier,the hydroxyl group in the inorganic zirconium hydrogen phosphate was modified by 3-aminopropyltrimethoxysilane. Then,the chiral Mn~Ⅲ( salen) was axially immobilized onto amine functionalized ZPS-PVPA. The immobilized catalyst were characterized by FTIR,DR UV-Vis,AAS,SEM,TEM,XPS,X-ray and EDS. The successful preparation of heterogeneous catalysts was confirmed. Subsequently,the catalytic performance of the supported catalyst for α-methylstyrene,styrene and indene was examined in detail. The results showed that the reaction was carried out at 0 ℃ for 3 h,the amount of catalyst was 0. 03 mmol,the e. e. value was 91. 5%with a 99% conversion when α-methylstyrene was investigated using m-chloroperoxybenzoic acid as oxidant and in the present of the axial ligand N-methylmorpholine nitrogen oxide( NMO). In addition,the recycling performance of the catalyst was examined using indene as a substrate. After 10 times of repeated use of the catalyst,the e. e. values( >90%) are significantly better than those achieved under a homogeneous counterparts( e. e. 65%).
Using zirconium poly( styrene-phenylvinyl-phosphonate)-phosphate( ZPS-PVPA) as a catalyst carrier,the hydroxyl group in the inorganic zirconium hydrogen phosphate was modified by 3-aminopropyltrimethoxysilane. Then,the chiral Mn~Ⅲ( salen) was axially immobilized onto amine functionalized ZPS-PVPA. The immobilized catalyst were characterized by FTIR,DR UV-Vis,AAS,SEM,TEM,XPS,X-ray and EDS. The successful preparation of heterogeneous catalysts was confirmed. Subsequently,the catalytic performance of the supported catalyst for α-methylstyrene,styrene and indene was examined in detail. The results showed that the reaction was carried out at 0 ℃ for 3 h,the amount of catalyst was 0. 03 mmol,the e. e. value was 91. 5%with a 99% conversion when α-methylstyrene was investigated using m-chloroperoxybenzoic acid as oxidant and in the present of the axial ligand N-methylmorpholine nitrogen oxide( NMO). In addition,the recycling performance of the catalyst was examined using indene as a substrate. After 10 times of repeated use of the catalyst,the e. e. values( >90%) are significantly better than those achieved under a homogeneous counterparts( e. e. 65%).
引文
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[6]Xiang S.,Zhang Y.,Xin Q.,Li C.,Chem.Commun.,2002,34(12),2696-2697
[7]Kureshy R.I.,Ahmad I.,Khan N.H.,Abdi S.H.R.,Pathak K.,Jasra R.V.,J.Catal.,2006,238(1),134-141
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[11]Ren W.S.,Fu X.K.,J.Mol.Catal.A:Chem.,2009,312(1/2),40-47
[12]Zou X.C.,Shi K.Y.,Chen S.C.,Fu X.K.,Chem.J.Chinese.Universities,2013,34(10),2319-2326(邹晓川,石开云,陈绍成,傅相锴.高等学校化学学报,2013,34(10),2319-2326)
[13]Zou X.C.,Fu X.K.,Li Y.D.,Tu X.B.,Fu S.D.,Luo Y.F.,Wu X.J.,Adv.Synth.Catal.,2010,352(1),163-170
[14]Zou X.C.,Fu X.K.,Luo Y.F.,Acta Chim.Sinica,2011,69(4),431-437(邹晓川,傅相锴,罗云飞.化学学报,2011,69(4),431-437)
[15]Zou X.C.,Wang C.,Wang Y.,Shi K.Y.,Wang Z.M.,Li D.W.,Fu X.K.,Polymers,2017,9(3),108-120
[16]Hu X.Y.,Fu,X.K.,Xu J.W.,Chem.J.Chinese Universities,2011,32(11),2605-2612(胡小艳,傅相锴,许江威.高等学校化学学报,2011,32(11),2605-2612)
[17]Huang J.,Fu X.K.,Wang G.,Miao Q.,Wang G.M.,Dalton Trans.,2012,41(35),10661-10669
[18]Huang X.M.,Fu X.K.,Jia Z.Y.,Miao Q.,Wang G.M.,Catal.Sci.Technol.,2013,3(2),415-424
[19]Huang J.,Tang M.,Li X.,Zhong G.Z.,Li C.M.,Dalton Trans.,2014,43(46),17500-17508
[20]Kim G.J.,Shin J.H.,Tetrahedron Lett.,1999,40(37),6827-6830
[21]Caplan N.A.,Hancock F.E.,Bulman P.P.C.,Hutchings G.J.,Angew.Chem.Int.Ed.,2004,43(13),1685-1688
[22]Venkataramanana N.S.,Rajagopal S.,Tetrahedron,2006,62(24),5645-5651
[23]Wu X.J.,Ma X.B.,Fu X.K.,Ji Y.L.,Wang Q.,Jia X.,J.Mol.Catal.A,2007,265(1/2),316-322