31 Topics in Organometallic Chemistry Editorial Board: M. Beller J. M. Brown P. H. Dixneuf l l A. Fu¨rstner L. S. Hegedus P. Hofmann l l T. Ikariya L. A. Oro M. Reetz Q.-L. Zhou l l l Topics in Organometallic Chemistry Recently Published Volumes TransitionMetalComplexesofNeutral MetalCatalyzedCascadeReactions h1-CarbonLigands VolumeEditor:T.J.J.Mu¨ller VolumeEditors:RemiChauvin,YvesCanac Vol.19,2006 Vol.30,2010 CatalyticCarbonylationReactions PhotophysicsofOrganometallics VolumeEditor:M.Beller VolumeEditor:AlistairJ.Lees Vol.18,2006 Vol.29,2010 MolecularOrganometallicMaterials BioorganometallicChemistry forOptics VolumeEditor:G.Simonneaux VolumeEditors:H.LeBozec,V.Guerchais Vol.17,2006 Vol.28,2010 SurfaceandInterfacialOrganometallic ConductingandMagneticOrganometallic ChemistryandCatalysis MolecularMaterials VolumeEditors:C.Cope´ret,B.Chaudret VolumeEditors:M.Fourmigue´,L.Ouahab Vol.16,2005 Vol.27,2009 MetalCatalystsinOlefinPolymerization ChiralDiazaligandsforAsymmetric VolumeEditor:Z.Guan Synthesis Vol.26,2009 VolumeEditors:M.Lemaire,P.Mangeney Vol.15,2005 Bio-inspiredCatalysts VolumeEditor:T.R.Ward PalladiuminOrganicSynthesis Vol.25,2009 VolumeEditor:J.Tsuji Vol.14,2005 DirectedMetallation VolumeEditor:N.Chatani MetalCarbenesinOrganicSynthesis Vol.24,2007 VolumeEditor:K.H.Do¨tz RegulatedSystemsforMultiphaseCatalysis Vol.13,2004 VolumeEditors:W.Leitner,M.Ho¨lscher Vol.23,2008 TheoreticalAspectsofTransitionMetal Catalysis OrganometallicOxidationCatalysis VolumeEditor:G.Frenking VolumeEditors:F.Meyer,C.Limberg Vol.12,2005 Vol.22,2007 N-HeterocyclicCarbenesinTransition RutheniumCatalystsandFineChemistry MetalCatalysis VolumeEditors:C.Bruneau,P.H.Dixneuf VolumeEditor:F.Glorius Vol.11,2004 Vol.21,2006 NewAspectsofZirconiumContaining DendrimerCatalysis OrganicCompounds VolumeEditor:L.H.Gade VolumeEditor:I.Marek Vol.20,2006 Vol.10,2004 C–X Bond Formation Volume Editor: Arkadi Vigalok With Contributions by (cid:1) (cid:1) (cid:1) Paul Bichler Moris S. Eisen David S. Glueck (cid:1) (cid:1) (cid:1) Lukas Hintermann Ariela W. Kaspi Jennifer A. Love Kilian Mun˜iz (cid:1) Andrei N. Vedernikov (cid:1) Arkadi Vigalok Editor Prof.ArkadiVigalok SchoolofChemistry TheSacklerFacultyofExactSciences TelAvivUniversity TelAviv69978 Israel [email protected] ISSN1436-6002 e-ISSN1616-8534 ISBN978-3-642-12072-5 e-ISBN978-3-642-12073-2 DOI10.1007/978-3-642-12073-2 SpringerHeidelbergDordrechtLondonNewYork LibraryofCongressControlNumber:2010926024 #Springer-VerlagBerlinHeidelberg2010 Thisworkissubjecttocopyright.Allrightsarereserved,whetherthewholeorpartofthematerialis concerned,specificallytherightsoftranslation,reprinting,reuseofillustrations,recitation,broadcasting, reproductiononmicrofilmorinanyotherway,andstorageindatabanks.Duplicationofthispublication orpartsthereofispermittedonlyundertheprovisionsoftheGermanCopyrightLawofSeptember9, 1965,initscurrentversion,andpermissionforusemustalwaysbeobtainedfromSpringer.Violations areliabletoprosecutionundertheGermanCopyrightLaw. Theuseofgeneraldescriptivenames,registerednames,trademarks,etc.inthispublicationdoesnot imply, even in the absence of a specific statement, that such names are exempt from the relevant protectivelawsandregulationsandthereforefreeforgeneraluse. Coverdesign:Ku¨nkelLopkaGmbH Printedonacid-freepaper SpringerispartofSpringerScience+BusinessMedia(www.springer.com) Volume Editor Prof.ArkadiVigalok SchoolofChemistry TheSacklerFacultyofExactSciences TelAvivUniversity TelAviv69978 Israel [email protected] Editorial Board Prof.MatthiasBeller Prof.PeterHofmann Leibniz-Institutfu¨rKatalysee.V. Organisch-ChemischesInstitut anderUniversita¨tRostock Universita¨tHeidelberg Albert-Einstein-Str.29a ImNeuenheimerFeld270 18059Rostock,Germany 69120Heidelberg,Germany [email protected] [email protected] Prof.JohnM.Brown Prof.TakaoIkariya ChemistryResearchLaboratory DepartmentofAppliedChemistry OxfordUniversity GraduateSchoolofScienceandEngineering MansfieldRd., TokyoInstituteofTechnology OxfordOX13TA,UK 2-12-1Ookayama,Meguro-ku, [email protected] Tokyo152-8550,Japan [email protected] Prof.PierreH.Dixneuf Prof.LuisA.Oro CampusdeBeaulieu Universite´deRennes1 InstitutoUniversitariodeCata´lisisHomoge´nea Av.duGlLeclerc DepartmentofInorganicChemistry 35042RennesCedex,France I.C.M.A.-FacultyofScience [email protected] UniversityofZaragoza-CSIC Zaragoza-50009,Spain Prof.AloisFu¨rstner [email protected] Max-Planck-Institutfu¨rKohlenforschung Prof.ManfredReetz Kaiser-Wilhelm-Platz1 Max-Planck-Institutfu¨rKohlenforschung 45470Mu¨lheimanderRuhr,Germany Kaiser-Wilhelm-Platz1 [email protected] 45470Mu¨lheimanderRuhr,Germany Prof.LouisS.Hegedus [email protected] DepartmentofChemistry Prof.Qi-LinZhou ColoradoStateUniversity StateKeyLaboratoryofElemento-organic FortCollins,Colorado80523-1872,USA Chemistry [email protected] NankaiUniversity WeijinRd.94,Tianjin300071PRChina [email protected] v Topics in Organometallic Chemistry Also Available Electronically Topics in Organometallic Chemistry is included in Springer’s eBook package ChemistryandMaterialsScience.Ifalibrarydoesnotoptforthewholepackagethe book series may be bought on a subscription basis. 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Aims and Scope The series Topics in Organometallic Chemistry presents critical overviews of researchresultsinorganometallicchemistry.Asourunderstandingoforganometallic structures,propertiesandmechanismsgrows,newpathsareopenedforthedesign of organometallic compounds and reactions tailored to the needs of such diverse areas as organic synthesis, medical research, biology and materials science. Thus the scope of coverage includes a broad range of topics of pure and applied organometallic chemistry, where new breakthroughs are being made that are of significance to a larger scientific audience. The individual volumes of Topics in Organometallic Chemistry are thematic. Reviewarticlesaregenerallyinvitedbythevolumeeditors. In references Topics in Organometallic Chemistry is abbreviated Top Organomet Chemandiscitedasajournal. vii Preface Reactions resulting in the formation of C–X bonds were undoubtedly among the firstexperimentsperformedbysyntheticorganicchemists.Withyears,thisareaof research hasmatured and nowadays reliesheavilyon the useoftransition metals. MostoftherecentresearchinC–Xbond-formingreactionshasbeenfocusedonthe late transition metal-catalyzed formation of aryl-nitrogen and aryl-oxygen bonds, reactions of primary importance to the pharmaceutical industry. Many highly efficient catalytic systems allowing for the formation of these bonds under mild conditionshavebeendevelopedandthoroughlyreviewed.Againstthisbackground, other C–X bond-forming reactions received considerably less attention. This volume is intended to highlight the recent advances in the formation of the C–X bondsotherthanaryl-oxygenoraryl-nitrogen. While not comprehensive, it presents seven balanced chapters that summarize the synthetic and mechanistic studies of the formation of C–P, C–S, C–Halide, C–N, and C–O bonds. The reviewed research areas demonstrate great variety of metals and reaction mechanisms that can be involved in the formation of these bonds. I believe that this scope will only grow in the near future thus providing importantinformationforchemistsinterestedinmakingC–Xbonds. As editor, I wish to express my gratitude to all the experts who contributed to thisvolume. TelAviv ArkadiVigalok ix Contents TransitionMetalCatalyzedElectrophilicHalogenation ofC–HBondsinAlpha-PositiontoCarbonylGroups ...................... 1 KilianMun˜iz LateTransitionMetal-MediatedFormationofCarbon–Halogen Bonds ........................................................................... 19 ArkadiVigalokandArielaW.Kaspi OrganometallicApproachestoCarbon–SulfurBondFormation ......... 39 PaulBichlerandJenniferA.Love RecentAdvancesinMetal-CatalyzedC–PBondFormation .............. 65 DavidS.Glueck C–OReductiveEliminationfromHighValentPtandPdCenters ...... 101 AndreiN.Vedernikov RecentDevelopmentsinMetal-CatalyzedAdditionsofOxygen NucleophilestoAlkenesandAlkynes ....................................... 123 LukasHintermann CatalyticC–N,C–O,andC–SBondFormationPromoted byOrganoactinideComplexes .............................................. 157 MorisS.Eisen Index .......................................................................... 185 xi TopOrganometChem(2010)31:1–18 DOI10.1007/978-3-642-12073-2_1 #Springer-VerlagBerlinHeidelberg2010 Transition Metal Catalyzed Electrophilic Halogenation of C–H Bonds in Alpha-Position to Carbonyl Groups KilianMun˜iz Abstract Transition metalsbearing chiral nonracemic ligands can actasefficient catalystsfortheselectivea-halogenationnexttocarbonylgroupsinorganicmole- cules. As a general reaction pattern, many of these reactions make use of 1,3- dicarbonyl or related functionalization readily, leading to enolization upon an interaction with Lewis acidic metal catalysts. Subsequent reaction with electro- philic halogenating reagents establishes the formation of new carbon-halogen bonds with asymmetric induction. This chapter discusses the state of the art of thesereactions,includingmechanisticdetailsregardingcatalyticcyclesandmodels for stereoselection. It also includes recent progresses on substrates other than 1,3-dicarbonyls,selectivemonohalogenationofmethylenegroupsandnewmecha- nisticpathways,suchastheuseofnucleophilicfluorinesources. Keywords Carbonyl compounds (cid:1) Catalysis (cid:1) Electrophilic substitution (cid:1) Halogenation(cid:1)Transitionmetals Contents 1 Introduction ................................................................................. 2 2 TransitionMetalCatalysts .................................................................. 3 2.1 TitaniumCatalysts .................................................................... 3 2.2 PalladiumCatalysts ................................................................... 6 2.3 NickelCatalysts...................................................................... 11 2.4 RutheniumCatalysts ................................................................. 14 2.5 OtherMetalCatalysts ................................................................ 15 3 Conclusion .................................................................................17 References ......................................................................................17 K.Mun˜iz Catalonian Institute for Chemical Investigation (ICIQ), Av. Pa¨ısos Catalans 16, Tarragona E-43007,Spain e-mail:[email protected]