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1、Chem.Rev.2004,104,2259-22832259SynthesisofHeterocyclesviaGroupVIFischerCarbeneComplexesJose´Barluenga,*JavierSantamarı´a,andMiguelToma´sInstitutoUniversitariodeQuı´micaOrganometa´lica“E.Moles”,UnidadAsociadaalCSIC,UniversidaddeOviedo,Julia´nClaverı´a,8,E-33006Oviedo,SpainReceivedNo
2、vember4,2003Contentsreportsfocusedontheutilityoftheseorganometalreagentsinthesynthesisofheterocycliccompounds1.Introduction2259haveactuallybeenreleased.Therefore,thepurpose2.SynthesisofNitrogenHeterocycles2259ofthisreviewistocalltheattentionofpeople2.1.HeterocyclizationsInvolvingth
3、eC-Cð-Bond2260involvedinorganicsynthesismediatedorcatalyzedofUnsaturatedCarbeneComplexesbyorganometallicreagentstothepotentialof2.1.1.Five-MemberedHeterocycles2260Fischer-typecarbenecomplexesforaccessingdiffer-2.1.2.Six-MemberedHeterocycles2262enttypesofheterocycles.Thereportwillbe
4、centered2.2.HeterocyclizationsInvolvingthe2263basicallyonsyntheticprocesseswhereineitheraMetal-CarbonDoubleBondcarbon-heteroatombondisformedoraheteroatom2.2.1.FromNitrogen-ContainingCarbene2263functionalityisdirectlyinvolved,thoughexamplesComplexesofintramolecularreactionsinvolving
5、substrateswith2.2.2.FromNitrogen-ContainingOrganic2267theheteroatominatetherchainarealsodisplayed.SubstratesThegeneralstructureofthemetalcarbenecom-3.SynthesisofOxygenHeterocycles2273plexesthatarereviewedisshowninFigure1.In3.1.PhotochemicalCyclizations2273mostcasesRappliesforalkyl,
6、aryl,orheteroaryl,X3.2.CyclizationsInitiatedbyAlkyneInsertion2274forORorNR2,andMforCr,Mo,W(structureA)or3.2.1.CyclizationswithoutIncorporationofCO2274Cr,W(structuresBandC).Amongthem,pentacar-3.2.2.CyclizationswithIncorporationofOne2275bonyl[alkenyl(methoxy)carbene]chromium(0)andtun
7、g-EquivalentofCOsten(0)complexes(typeB,M)Cr,W;X)OMe)have3.2.3.CyclizationswithIncorporationofTwo2277certainlybecomethemostpowerfulsystems,atleastEquivalentsofCOintermsofreactivity.3.3.CyclizationsInvolvingC-HInsertion2278Thisreportisdividedintofourmainpartsaccord-3.4.CyclizationsIn
8、itiatedbyNucleophilicAttac
