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1、Computationalstudyofunprecedentedpalladium-catalyzedaminationofchloromethylnaphthalenewithpyrrolidine#5101520WANGQin,JIAJianfeng,WUHaishun**(SchoolofChemistryandMaterialsScience,ShanxiNormalUniversity,Linfen041004)Abstract:Thereductiveeliminationintheaminationr
2、eactionsofchloromethylnaphthalenewithpyrrolidinebyPd(0)complexeshavebeentheoreticallystudiedwiththedensityfunctionaltheory.Ourstudiesindicatesthattherearetwopossiblereactionpathwaysfromthetwoconformers.Bothtwopathwaysinvolvesthreemajorsteps:theisomerizationfromη1
3、-menaphthylcomplextoη3-menaphthylcomplex,theη3-menaphthylrearrangementfromη3-exo-menaphthylcomplextoη3-endo-menaphthylcomplex,andmigratoryinsertionofamino-grouptonaphthyl.OnthebasisoftheDFTcalculations,wefoundthatproductofaminationisortho-aminatedproductkinetical
4、lyandpara-aminatedproductthermodynamically.Itisnotedthatthetetrahydrofuranassolventdoesnotchangethetrendsofthepotentialenergysurfacecomparedtothatfoundinthegasphase.Keywords:Densityfunctionaltheory;Palladadium;Amination;Regioselectivity0IntroductionThedevelopment
5、ofconvenientandefficientmethodsfortheformationofC-Nbondhasattachedconsiderableattention,especiallytheformationofC(aryl)-Nbond.Arylaminesarepartofmoleculeswithstructurallyinterestingproperties,andofmaterialswithimportantelectronicandmechanicalproperties[1-3].Thetr
6、ansition-metal-catalyzedaminationofarylhalideswithaminesandamidesusingpalladium[4-8],copper[9-15],nickel[16-20],andiron[21,22]catalystshasrecentlyprovedtobeapowerfulmethodforformationofanewC(aryl)-Nbond.Bycomparison,verylittle253035knownabouttheformationoftheC
7、(alkyl)-Nbond.ThereareafewreportsabouttheformationofC(alkyl)-Nbondcatalyzedbyplatinum[23],nickel[24,25],palladium[26-28]complexes.Inaddition,anexcellentworkbyHartwigandcoworkersrevealedthatthereductiveeliminationreactionofabenzylpalladiumamidocomplexcontainingthe
8、chelatingligandcaneasilyoccurtoformaC(alkyl)-Nbondinbenzylamine[29].Thecatalyticaminationofarylhalidesusuallyoccursatthearomaticcarbonlinkedtoahalogenatom,assh
