PdCl_2催化芳基硼酸与溴代芳烃Suzuki-Miyaura偶联反应的机理研究
详细信息    查看全文 | 推荐本文 |
  • 英文篇名:Research on the mechanism of Suzuki-Miyaura coupling reaction of aryl boric acid with aryl bromide catalyzed by PdCl_2
  • 作者:黄平 ; 王薇 ; 李来才 ; 兰子平
  • 英文作者:HUANG Ping;WANG Wei;LI Lai-Cai;LAN Zi-Ping;Panzhihua University;Sichuan province Key Laboratory of Vanadium & Titanium Resource Comprehensive Utilization;College of Chemistry and Material Science,Sichuan Normal University;College of Chemistry and Chemical Engineering,Neijing Normal University;
  • 关键词:密度泛函理论 ; Suzuki-Miyaura偶联反应 ; 反应机理 ; 过渡态
  • 英文关键词:Density functional theory;;Suzuki-Miyaura coupling reaction;;Reaction mechanism;;Transition state
  • 中文刊名:YZYF
  • 英文刊名:Journal of Atomic and Molecular Physics
  • 机构:攀枝花学院;四川省钒钛材料工程技术研究中心;四川师范大学化学与材料学院;四川内江师范学院化学化工学院;
  • 出版日期:2017-10-28
  • 出版单位:原子与分子物理学报
  • 年:2017
  • 期:v.34
  • 语种:中文;
  • 页:YZYF201705004
  • 页数:6
  • CN:05
  • ISSN:51-1199/O4
  • 分类号:27-32
摘要
采用密度泛函理论(DFT)中的M06方法,以二甲基甲酰胺(DMF)溶剂,研究了无催化剂、PdCl_2为催化剂催化芳基硼酸与溴代芳烃的交叉偶联反应的反应机理.使用6-311+G*基组(Pd采用赝势基组Lan L2DZ)对芳基硼酸与溴代芳烃Suzuki-Miyaura偶联反应过程中所有反应物、中间体、过渡态和产物的几何构型进行了优化,同时进行了频率计算,各过渡态都有唯一虚频,确认了中间体和过渡态的合理性;通过自然键轨道(NBO)理论和分子内原子理论(AIM)理论分析了分子轨道间的相互作用.结果发现:在没有催化剂的条件下,Suzuki-Miyaura偶联反应形成的反应速控步骤活化能为49.70 kcal/mol,在PdCl_2催化作用下,反应速控步骤活化能为31.08 kcal/mol,比较研究结果,PdCl_2能有效催化该反应的进行,我们的研究结果与实验结果相吻合.
        Using the density functional theory( DFT) M06 method,we studied the reaction mechanism of the cross coupling reaction of aryl boric acid with aryl bromide catalyzed by PdCl_2 and no catalyst. Under the basis set level of 6-311 + G( d,p)( Pd using the pseudo potential basis set of LanL2DZ),we optimized the configuration of all the reactants,transition states,intermediates and products of Suzuki-Miyaura coupling reaction with aryl boronic acid and aryl bromide. Meanwhile,we calculated the frequency and found out that all the transient states has the only imaginary frequency; moreover,we confirmed the rationality of intermediates and transient states. We analyzed the interaction among molecular orbits via natural bond orbital( NBO) and atoms in molecules( AIM). The results showed that the Suzuki Miyaura coupling reaction rate-determing energy of no catalyst is 49. 70 kcal/mol and that with PdCl_2 is 31. 08 kcal/mol. Comparing the results,PdCl_2 can effectively catalyze the reaction. Our results are in accordance with the experimental results.
引文
[1]Miyaura N,Yamada K,Suzuki A.A new stereospecific cross-coupling by the palladium-catalyzed reaction of 1-alkenylboranes with 1-alkenyl or 1-alkynyl halides[J].Tetrahedron Lett.,1979,20:3437.
    [2]Miyaura N,Suzuki A,Miyaura N,et al.Stereoselective synthesis of arylated(E)-alkenes by the reaction of alk-1-enylboranes with aryl halides in the presence of palladium catalyst[J].J.Chem.Soc.Chem.Commun.,1979,19:866.
    [3]Yu Q F,Zhang Y H,Yin Q,et al.Electrophilic ipso-Iodocyclization of N-(4-Methylphenyl)propiolamides:Selective Synthesis of 8-Methyleneazaspiro[4,5]trienes[J].J.Org.Chem.,2008,73:3658.
    [4]Miyaura N,Yanagi T,Suzuki A.The palladium-catalyzed cross-coupling reaction of phenylboronic acid with haloarenes in the presence of bases[J].Synth.Commun.,1981,11:513.
    [5]Schnyder A,Indolese A F,Studer M,et al.A new generation of air stable,highly active Pd complexes for C-C and C-N coupling reactions with aryl chlorides[J].Angew Chem.Int.Ed.Engl.,2002,41:3668.
    [6]Mathews C J,Smith P J,Welton T.Palladium catalyzed Suzuki cross-coupling reeactions in ambient temperature ionic liquids[J].Chem.Commun.,2000,14:1249.
    [7]Mckeown B A,Gonzalez H E,Friedfeld M R,et al.Mechanistic studies of ethylene hydrophenylation catalyzed by bipyridyl Pt(II)complexes[J].J.Am.Chem.Soc.,2011,133:31.
    [8]Yuan Q L,Zhou X T,Ji H B.Efficient oxidative coupling of amines to imines catalyzed by manganese(III)meso-tetraphenylporphyrin chloride under ambient conditions[J].Catal.Commun.,2010,12:202.
    [9]Zhang L,Zheng Y,Pan X X,et al.Investigation the reaction mechanism from phenylacetaldehyde and benzylamine to polysubstituted imidazole catalyzed by I2[J].Chin.J.Org.Chem.,2014,8:1595(in Chinese)[张林,郑妍,潘晓晓,等.碘催化苯乙醛与苄胺合成多取代咪唑的反应机理研究[J].有机化学,2014,8:1595]
    [10]Becke A D.Density-functional thermochemistry.III.The role of exact exchange[J].J.Chem.Phys.,1993,98:5648.
    [11]Lee C,Yang W,Parr R G.Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density[J].Phy.Rev.B,1988,37:785.
    [12]Miehlich B,Savin A,Stoll H,et al.Results obtained with the correlation energy density functionals of Becke and Lee,Yang and Parr[J].Chem.Phys.Lett.,1989,157:200.
    [13]Gonzalez C,Schlegel H B.An improved algorithm for reaction path following[J].J.Chem.Phys.,1989,90:2154.
    [14]Gonzalez C,Schlegel H B.Reaction path following in mass-weighted internal coordinates[J].J.Phys.Chem.C,1990,94:5523.
    [15]Reed A E,Weinhold F,Curtiss L A.Intermolecular interactions from a natural bond orbital,donor-acceptor viewpoint[J].Chem.Rev.,1988,88,899.
    [16]Bader R W F.Atoms in Molecules:A Quantum Theory[M].Oxford:Oxford University Press,1990.
    [17]Frisch M J,Trucks G W,Schlegel H B,et al.Gaussian 09,Rev.A.02,Wallingford CT:Gaussian,Inc.,2009.

© 2004-2018 中国地质图书馆版权所有 京ICP备05064691号 京公网安备11010802017129号

地址:北京市海淀区学院路29号 邮编:100083

电话:办公室:(+86 10)66554848;文献借阅、咨询服务、科技查新:66554700