Topics in Organometallic Chemistry 46 Marc Taillefer Dawei Ma Editors Amination and Formation of sp2 C–N Bonds 46 Topics in Organometallic Chemistry Editorial Board: M. Beller J. M. Brown P. H. Dixneuf l l J. Dupont A. Fu¨rstner L. J. Gooßen l l P. Hofmann T. Ikariya S. Nolan l l L. A. Oro Q.-L. Zhou l Topics in Organometallic Chemistry Recently Published Volumes Alkaline-EarthMetalCompounds: HigherOxidationStateOrganopalladium OdditiesandApplications andPlatinumChemistry VolumeEditor:SjoerdHarder VolumeEditor:A.J.Canty Vol.45,2013 Vol.35,2011 InventingReactions IridiumCatalysis VolumeEditor:LukasJ.Gooßen VolumeEditor:P.G.Andersson Vol.44,2013 Vol.34,2011 IronCatalysis–Fundamentalsand Hydrofunctionalization Applications VolumeEditors:ValentineP.Ananikov, VolumeEditor:B.Plietker MasatoTanaka Vol.33,2011 Vol.43,2013 MedicinalOrganometallicChemistry OrganometallicsasCatalysts VolumeEditors:G.Jaouen,N.Metzler-Nolte intheFineChemicalIndustry Vol.32,2010 VolumeEditors:MatthiasBeller, Hans-UlrichBlaser C-XBondFormation Vol.42,2012 VolumeEditor:A.Vigalok Vol.31,2010 ModernOrganoaluminumReagents: TransitionMetalComplexesofNeutral Preparation,Structure,ReactivityandUse h1-CarbonLigands VolumeEditors:SimonWoodward, VolumeEditors:R.Chauvin,Y.Canac SamuelDagorne Vol.30,2010 Vol.41,2012 PhotophysicsofOrganometallics OrganometallicPincerChemistry VolumeEditor:A.J.Lees VolumeEditors:GerardvanKoten, Vol.29,2010 DavidMilstein Vol.40,2012 MolecularOrganometallicMaterials forOptics OrganometallicsandRenewables VolumeEditors:H.LeBozec,V.Guerchais VolumeEditors:MichaelA.R.Meier, Vol.28,2010 BertM.Weckhuysen,PieterC.A.Bruijnincx ConductingandMagneticOrganometallic Vol.39,2012 MolecularMaterials TransitionMetalCatalyzedEnantioselective VolumeEditors:M.Fourmigue´,L.Ouahab AllylicSubstitutioninOrganicSynthesis Vol.27,2009 VolumeEditor:UliKazmaier MetalCatalystsinOlefinPolymerization Vol.38,2011 VolumeEditor:Z.Guan BifunctionalMolecularCatalysis Vol.26,2009 VolumeEditors:T.Ikariya,M.Shibasaki Bio-inspiredCatalysts Vol.37,2011 VolumeEditor:T.R.Ward Vol.25,2009 AsymmetricCatalysisfromaChinese Perspective DirectedMetallation VolumeEditor:ShengmingMa VolumeEditor:N.Chatani Vol.36,2011 Vol.24,2007 Amination and Formation 2 of sp C–N Bonds Volume Editors: Marc Taillefer and Dawei Ma With Contributions by (cid:1) (cid:1) (cid:1) (cid:1) C. Bolm S. Bhargava A. Correa Y. Jiang (cid:1) (cid:1) (cid:1) (cid:1) M.L. Kantam G.S. Lemen D. Ma F. Monnier (cid:1) (cid:1) (cid:1) C. Venkat Reddy P. Srinivas M. Taillefer J.P. Wolfe Editors MarcTaillefer DaweiMa EcoleNationaleSuperieuredeChimie ShanghaiInstituteofOrganicChemistry (CNRS) ChineseAcademyofSciences Montpellier Shanghai France People’sRepublicofChina ISSN1436-6002 ISSN1616-8534(electronic) ISBN978-3-642-40545-7 ISBN978-3-642-40546-4(eBook) DOI10.1007/978-3-642-40546-4 SpringerHeidelbergNewYorkDordrechtLondon LibraryofCongressControlNumber:2013956808 #Springer-VerlagBerlinHeidelberg2013 Thisworkissubjecttocopyright.AllrightsarereservedbythePublisher,whetherthewholeorpartof the material is concerned, specifically the rights of translation, reprinting, reuse of illustrations, recitation,broadcasting,reproductiononmicrofilmsorinanyotherphysicalway,andtransmissionor informationstorageandretrieval,electronicadaptation,computersoftware,orbysimilarordissimilar methodologynowknownorhereafterdeveloped.Exemptedfromthislegalreservationarebriefexcerpts inconnectionwithreviewsorscholarlyanalysisormaterialsuppliedspecificallyforthepurposeofbeing enteredandexecutedonacomputersystem,forexclusiveusebythepurchaserofthework.Duplication ofthispublicationorpartsthereofispermittedonlyundertheprovisionsoftheCopyrightLawofthe Publisher’s location, in its current version, and permission for use must always be obtained from Springer.PermissionsforusemaybeobtainedthroughRightsLinkattheCopyrightClearanceCenter. ViolationsareliabletoprosecutionundertherespectiveCopyrightLaw. Theuseofgeneraldescriptivenames,registerednames,trademarks,servicemarks,etc.inthispublication doesnotimply,evenintheabsenceofaspecificstatement,thatsuchnamesareexemptfromtherelevant protectivelawsandregulationsandthereforefreeforgeneraluse. Whiletheadviceandinformationinthisbookarebelievedtobetrueandaccurateatthedateofpublication, neithertheauthorsnortheeditorsnorthepublishercanacceptanylegalresponsibilityforanyerrorsor omissionsthatmaybemade.Thepublishermakesnowarranty,expressorimplied,withrespecttothe materialcontainedherein. Printedonacid-freepaper SpringerispartofSpringerScience+BusinessMedia(www.springer.com) Preface Theuseoftransitionmetalcatalysishasprovidedorganicchemistswithawideand quasi-exhaustive toolbox to create selectively the C(sp2)-N bonds, essential not onlyforthedevelopmentofbioactivemoleculesbutalsoformaterialsengineering. Drawing on the bountiful number of publications related to this topic in the last 10years,thisvolumemainlyfocusesonthemostsignificantresultsandimportant breakthroughs. The volume highlights in the first chapter, written by Lemen and Wolfe, the discoveryandthedevelopmentoforiginalpalladium-basedcatalystsforC(sp2)-N bondformationvia thecoupling ofnitrogennucleophilesandaryl/alkenylhalides and pseudohalides. The authors also report various applications of these transfor- mationstothesynthesisofusefulcompounds,includingbiologicallyactivemole- culesandmaterials. In the second chapter, Correa and Bolm discuss a powerful set of protocols involvingC(sp2)-Nbondformationwhichhaveemergedasreliableandconvenient alternativesfortheassemblyofenaminesandenamides.Theauthorsalsodescribe palladium-catalyzed oxidative amination of alkenes and both palladium- and copper-catalyzedcross-couplingsgenerallybetweenvinylhalidesorpseudohalides andaminesoramides. Owing to their importance for pharmaceutical and material sciences, N-containing heterocycles have received great attention from the synthetic com- munity. Another masterpiece of this volume “Assembly of N-Containing Hetero- cycles via Pd and Cu-Catalyzed C–N Bond Formation Reactions”, presented by JiangandMa,coverstheoriginalandlastcontributionsonthedevelopmentofPd- and Cu-catalysts for the assembly of N-heterocycles such as indoles, benzimida- zoles, pyrroles, indazoles, indolines, lactams, quizolinones, heterobenzazepines, andotherN-containingheterocycles. By far the greatest number of reports on the modern catalytic Ullmann-type reactionshasdealtwiththecreationofC–Nbonds.Kantametal.present,intheir chapter, the recent developments in heterogeneous or recyclable copper-catalysts availabletoselectivelyformthisC(sp2)-Nbond.Thechallengesandopportunities v vi Preface incopper-catalyzedheterogeneouscatalysisareenormousaslessresearchhasbeen carried out in this area compared to homogeneous systems. This part covers the recentrecyclableprotocolsfortheC(cid:3)Nbondformingreactionsbetweenaromatic, heterocyclic, and aliphatic-amines with aryl iodides, bromides, chlorides, and arylboronicacidsemployingcoppermediatedsystems. The last chapter by Monnier and Taillefer focuses on the copper-catalyzed formation of C(sp2)-N bond via the coupling of nitrogen nucleophiles (N-heterocycles, amines, anilines, amides, ammonia, azides, hydroxylamines, nitrites salts, phosphonic amides) with aryl halides. The authors also present C (aryl)–Nbondformationasaresultofthecouplingbetweenthesenucleophilesand aryl-boronicacids(theChan–Lamreaction). Wewouldliketothanktheauthorsfortheirdiligentworkonthishottopic. Montpellier,France MarcTaillefer Shanghai,China DaweiMa Contents Palladium-Catalyzedsp2C–NBondFormingReactions:Recent DevelopmentsandApplications ............................................... 1 GeorgiaS.LemenandJohnP.Wolfe Metal-CatalyzedC(sp2)–NBondFormation ................................ 55 ArkaitzCorreaandCarstenBolm AssemblyofN-ContainingHeterocyclesviaPd-andCu-Catalyzed C–NBondFormationReactions ............................................. 87 YongwenJiangandDaweiMa RecentDevelopmentsinRecyclableCopperCatalystSystems forC–NBondFormingCross-CouplingReactionsUsing ArylHalidesandArylboronicAcids ........................................ 119 MannepalliLakshmiKantam,ChintareddyVenkatReddy, PottabathulaSrinivas,andSureshBhargava Copper-CatalyzedC(aryl)–NBondFormation ............................ 173 FlorianMonnierandMarcTaillefer Index .......................................................................... 205 vii TopOrganometChem(2013)46:1–54 DOI:10.1007/3418_2012_56 #Springer-VerlagBerlinHeidelberg2012 Publishedonline:13February2013 Palladium-Catalyzed sp2 C–N Bond Forming Reactions: Recent Developments and Applications GeorgiaS.LemenandJohnP.Wolfe Abstract ThisreviewdescribesrecentdevelopmentsinthefieldofPd-catalyzedsp2 C–Nbondformationthatwerereportedintheprimaryliteraturebetween2004and 2008. These transformations have found widespread application in both academia andindustry.Abriefhistoryofthefieldispresented,followedbyrecentimprovements and extensions of the methodology. Applications of these transformations to the synthesisofusefulcompounds,includingbiologicallyactivemolecules,andmaterials, aredescribed. Keywords Arylamines(cid:1)Cross-coupling(cid:1)Heterocycles(cid:1)Materials(cid:1)N-Arylation(cid:1) Naturalproducts Contents 1 IntroductionandScope....................................................................... 2 2 EarlyWorkPriorto2004.................................................................... 2 3 ImprovementsandExtensionsofPd-CatalyzedN-ArylationMethods.................... 6 3.1 NewLigandsandContinuedExploration ofExistingLigands..................................................................... 6 3.2 ModifiedReactionConditionsorTechniquesThatFacilitatePd-Catalyzed N-Arylations............................................................................ 13 3.3 NewNucleophilesandElectrophilesorImprovedReactionsofPreviously StudiedNucleophilesandElectrophiles............................................... 13 4 Applications.................................................................................. 24 4.1 SynthesisofHeterocyclesviaReactionSequencesInvolvingN-Arylation.......... 24 4.2 SynthesisofNaturalProductsandPharmaceuticalTargetMolecules............... 27 4.3 SynthesisofMoleculeswithPotentialMaterialsChemistryApplications........... 30 4.4 UseofN-ArylationReactionsfortheSynthesisofLigandsforMetalComplexesand Catalysts................................................................................ 38 4.5 ProcessScaleApplicationsofPd-CatalyzedN-ArylationReactions................. 40 5 Conclusion.................................................................................... 42 References........................................................................................ 42 G.S.LemenandJ.P.Wolfe(*) DepartmentofChemistry,UniversityofMichigan,AnnArbor,MI48109-1055,USA e-mail:[email protected] 2 G.S.LemenandJ.P.Wolfe Abbreviations mW Microwave Cy Cyclohexyl Dba Dibenzylideneacetone Dppe 1,2-Bis(diphenylphosphinoethane) Dppp 1,3-Bis(diphenylphosphinopropane) Hex n-Hexyl HMDS Hexamethyldisilazide IPr N,N0-Bis(2,6-diisopropylphenyl)imadalol-2-ylidene i-Pr Isopropyl PMP 4-Methoxyphenyl SAR Structure–activityrelationship TBS tert-Butyldimethylsilyl 1 Introduction and Scope MoleculesthatcontainarylC–Nbondsplayimportantrolesinmanydifferentareasof chemistry,includingmaterialsandpharmaceuticals.Forexample,anumberoftop- sellingdrugs,includingLipitor[1],Abilify[2],andCelebrex[3],containthisfunc- tional unit. Over the past 15 years, Pd-catalyzed coupling reactions between aryl halidesandamineshavedevelopedintobroadlyutilizedmethodsforsp2C–Nbond formation.Thesetransformationshavebeenusedonbothsmallacademicscalesand verylargeindustrialscales.Duetothesignificanceofthisfield,anumberofreviews havebeenpreviouslypublisheddescribingvariousstagesofitsdevelopment([4–11]; foracomprehensivereviewontheBuchwaldbiarylphosphineligands,see[12];fora reviewontheutilityofJosiphos-typeligandsinPd-catalyzedN-arylationreactions, see [13];[14–21]). Thisreviewoutlines key aspects ofPd-catalyzedsp2 C–Nbond formingcross-couplingreactionsofnitrogennucleophilesandaryl/alkenylhalidesand pseudohalidesthatwerereportedintheliteraturebetween2004and2008.Although this review is focused primarily on synthetic aspects of the chemistry, a very brief descriptionofreactionmechanismalongwithabriefhistoricalbackgroundisprovided toplacethecurrentworkincontextandaidthereader. 2 Early Work Prior to 2004 The first example ofthe formationofan aryl C–N bond via a Pd-catalyzed cross- couplingreactionofanarylhalidewasreportedin1983byMigitaandcoworkers [22,23].Duringthecourseoftheirstudiesonthereactivityoforganotincompounds,