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1、中国科技论文在线http://www.paper.edu.cnComputationalstudyofunprecedentedpalladium-catalyzedaminationofchloromethylnaphthalenewithpyrrolidine#5101520WANGQin,JIAJianfeng,WUHaishun**(SchoolofChemistryandMaterialsScience,ShanxiNormalUniversity,Linfen041004)Abstract:Thereductiveeliminationi
2、ntheaminationreactionsofchloromethylnaphthalenewithpyrrolidinebyPd(0)complexeshavebeentheoreticallystudiedwiththedensityfunctionaltheory.Ourstudiesindicatesthattherearetwopossiblereactionpathwaysfromthetwoconformers.Bothtwopathwaysinvolvesthreemajorsteps:theisomerizationfromη1-me
3、naphthylcomplextoη3-menaphthylcomplex,theη3-menaphthylrearrangementfromη3-exo-menaphthylcomplextoη3-endo-menaphthylcomplex,andmigratoryinsertionofamino-grouptonaphthyl.OnthebasisoftheDFTcalculations,wefoundthatproductofaminationisortho-aminatedproductkineticallyandpara-aminatedpr
4、oductthermodynamically.Itisnotedthatthetetrahydrofuranassolventdoesnotchangethetrendsofthepotentialenergysurfacecomparedtothatfoundinthegasphase.Keywords:Densityfunctionaltheory;Palladadium;Amination;Regioselectivity0IntroductionThedevelopmentofconvenientandefficientmethodsforthe
5、formationofC-Nbondhasattachedconsiderableattention,especiallytheformationofC(aryl)-Nbond.Arylaminesarepartofmoleculeswithstructurallyinterestingproperties,andofmaterialswithimportantelectronicandmechanicalproperties[1-3].Thetransition-metal-catalyzedaminationofarylhalideswithamin
6、esandamidesusingpalladium[4-8],copper[9-15],nickel[16-20],andiron[21,22]catalystshasrecentlyprovedtobeapowerfulmethodforformationofanewC(aryl)-Nbond.Bycomparison,verylittle253035knownabouttheformationoftheC(alkyl)-Nbond.ThereareafewreportsabouttheformationofC(alkyl)-Nbondcatal
7、yzedbyplatinum[23],nickel[24,25],palladium[26-28]complexes.Inaddition,anexcellentworkbyHartwigandcoworkersrevealedthatthereductiveeliminationreactionofabenzylpalladiumamidocomplexcontainingthechelatingligandcaneasilyoccurtoformaC(alkyl)-Nbondinbenzylamine[29].Thecatalyticaminatio
8、nofarylhalidesusuallyoccursatthearomatic
