mechanism, regioselectivity, and the kinetics

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1、FULLPAPERDOI:10.1002/chem.200701725Mechanism,Regioselectivity,andtheKineticsofPhosphine-Catalyzed[3+2]CycloadditionReactionsofAllenoatesandElectron-DeficientAlkenes[a][a][a,b][b,c][a]YongLiang,SongLiu,YuanzhiXia,YahongLi,andZhi-XiangYu*Abstract:Withtheaidofcomputations

2、alyzed[3+2]cycloadditionreactionoftheories.Isotopiclabelingexperimentsandexperiments,thedetailedmecha-allenoatesandelectron-deficiental-combinedwithDFTcalculationsnismofthephosphine-catalyzed[3+2]kenes.DFTcalculationsandFMOshowedthatthecommonlyacceptedcycloadditionreac

3、tionsofallenoatesanalysisrevealedthatanelectron-with-intramolecular[1,2]-protonshiftshouldandelectron-deficientalkeneshasbeendrawinggroupisrequiredintheallenebecorrectedtoawater-catalyzed[1,2]-investigated.Itwasfoundthatthisre-toensurethegenerationofthe1,3-protonshift.

4、Additionalisotopiclabel-actionincludesfourconsecutivepro-dipolekineticallyandthermodynami-ingexperimentsofthehetero-[3+2]cesses:1)Insitugenerationofa1,3-cally.Atoms-in-molecules(AIM)cycloadditionofallenoatesandelec-dipolefromallenoateandphosphine,theorywasusedtoanalyze

5、thestabilitytron-deficientiminesfurthersupport2)stepwise[3+2]cycloaddition,3)aofthe1,3-dipole.Theregioselectivitythisfinding.Thisinvestigationhasalsowater-catalyzed[1,2]-hydrogenshift,ofthe[3+2]cycloadditioncanbera-beenextendedtothestudyoftheand4)eliminationofthephosph

6、inetionalizedverywellbyFMOandAIMphosphine-catalyzed[3+2]cycloaddi-catalyst.Insitugenerationofthe1,3-tionreactionofalkynoatesasthedipoleiskeytoallnucleophilicphos-three-carbonsynthon,whichshowedKeywords:allenes·densityfunc-phine-catalyzedreactions.Throughathatthegenerat

7、ionofthe1,3-dipoleintionalcalculations·kinetics·phos-kineticstudywehaveshownthatthethisreactionalsooccursbyawater-cat-phineorganocatalysis·reactiongenerationofthe1,3-dipoleistherate-alyzedprocess.mechanismsdeterminingstepofthephosphine-cat-[1,2]Introductionconstruction

8、offive-memberedheterocycles.InspiredbythesuccessofHuisgenschemistryandothercycloadditionTheHuisgen[3+2]cycloaddition