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Metal Free C-H Functionalization of Aromatics: Nucleophilic Displacement of Hydrogen PDF

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Topics in Heterocyclic Chemistry 37 Series Editors: B.U.W. Maes · J. Cossy · S. Polanc Valery Charushin Oleg Chupakhin Editors Metal Free C–H Functionalization of Aromatics Nucleophilic Displacement of Hydrogen 37 Topics in Heterocyclic Chemistry SeriesEditors: B.U.W. Maes, Antwerpen, Belgium Janine Cossy, Paris, France Slovenko Polanc, Ljubljana, Slovenia Editorial Board: D. Enders, Aachen, Germany S.V. Ley, Cambridge, UK G. Mehta, Bangalore, India K.C. Nicolaou, La Jolla, CA, USA R. Noyori, Hirosawa, Japan L.E. Overmann, Irvine, CA, USA A. Padwa, Atlanta, GA, USA Aims and Scope The series Topics in Heterocyclic Chemistry presents critical reviews on present andfuturetrendsintheresearchofheterocycliccompounds.Overallthescopeisto covertopicsdealingwithallareaswithinheterocyclicchemistry,bothexperimental andtheoretical,ofinteresttothegeneralheterocyclicchemistrycommunity. The series consists of topic related volumes edited by renowned editors with contributionsofexpertsinthefield. More information about this series at http://www.springer.com/series/7081 Valery Charushin • Oleg Chupakhin Editors Metal Free C–H Functionalization of Aromatics Nucleophilic Displacement of Hydrogen With contributions by V.N. Charushin • O.N. Chupakhin • I. Gallardo • G. Guirado • A.V. Gulevskaya • Y. Kondo • M. Ma˛kosza • A.F. Pozharskii • S. Shevelev • A. Starosotnikov • K. Wojciechowski Editors ValeryCharushin OlegChupakhin PostovskyInstituteofOrganicSynthesis; PostovskyInstituteofOrganicSynthesis; UralFederalUniversity UralFederalUniversity Ekaterinburg Ekaterinburg Russia Russia ISSN1861-9282 ISSN1861-9290(electronic) ISBN978-3-319-07018-6 ISBN978-3-319-07019-3(eBook) DOI10.1007/978-3-319-07019-3 SpringerChamHeidelbergNewYorkDordrechtLondon LibraryofCongressControlNumber:2014946582 #SpringerInternationalPublishingSwitzerland2014 Thisworkissubjecttocopyright.AllrightsarereservedbythePublisher,whetherthewholeorpart of 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. The use of general descriptive names, registered names, trademarks, service marks, etc. in this publicationdoesnotimply,evenintheabsenceofaspecificstatement,thatsuchnamesareexempt fromtherelevantprotectivelawsandregulationsandthereforefreeforgeneraluse. While the advice and information in this book are believed to be true and accurate at the date of publication,neithertheauthorsnortheeditorsnorthepublishercanacceptanylegalresponsibilityfor anyerrorsoromissionsthatmaybemade.Thepublishermakesnowarranty,expressorimplied,with respecttothematerialcontainedherein. Printedonacid-freepaper SpringerispartofSpringerScience+BusinessMedia(www.springer.com) Preface One ofthe current trends indevelopment ofboth academic andindustrialorganic synthesis is orientation of chemists on using “chlorine-free” ecologically benign processes, based on direct methods of C–H functionalization of aromatic compounds,avoidinghalogenatedstartingmaterialsorintermediates. Thesynthesisandstructuralmodificationsofaromaticsystemshavealwaysbeen asubjectofconsiderableinteresttomanychemists.Electrophilicaromaticsubsti- tution of hydrogen S Ar and nucleophilic aromatic substitution of halogen and E other good leaving anionic groups S Aripso, became the main synthetic N methodologiesandbasicindustrialprocessesofthelastcentury.Formanydecades theyhavebeenexploitedbychemiststoobtainenormousnumberofderivativesof thisimportantclassoforganiccompounds. A great variety of effective metal-catalyzed cross-coupling reactions (Heck, Stille, Suzuki-Mijaura, Sonogashira, Kumada, Negishi, Buchwald-Hartwig, Hijama, and others) have been advanced during the last three decades, however mostofthesecatalyticmethodsarealsobasedonusingarylhalogenides,asstarting materials.Thesituationisfarfromidealfromanatomeconomypointofview(for instance, bromination of aromatics – debromination), to say nothing of its poor correspondence to other principles of the green chemistry. Besides that, metal- catalyzed cross-coupling reactions often require the presence of palladium- containingcatalysts andphosphorus-containingligands,tracesofwhich couldnot be admitted in pharmaceutical products. This is why the roundtable of leading globalpharmaceuticalcompanies,arrangedbytheAmericanChemicalSocietyand Green Chemistry Institute, put the C–H activation of aromatics (including cross- coupling reactions, avoiding the preparation of haloaromatics) in the list of promising“aspirational”reactions(fordetailsee:[1]). Webelievethatitisahightimetodrawattentionofbothacademicandindustrial chemists to a relatively new synthetic methodology, which is based on the direct metal-freenucleophilicdisplacementofhydrogeninaromaticsystems(S H). N This volume of Topics in Heterocyclic Chemistry is composed of six chapters presented by an international set of authors, which responded to our proposal to v vi Preface review the recently published data on the S H reactions, proceeding without N organometallicintermediates. The chapter “Metal-Free С–Н Functionalization of Aromatic Compounds Through the Action of Nucleophilic Reagents” by Valery Charushin and Oleg Chupakhin (Postovsky Institute of Organic Synthesis; Ural Federal University, Ekaterinburg, Russia) presents a general concept of the S H reactions. It is sup- N posed to demonstrate a common character of the S H reactions, as a fundamental N property of aromatic and hetero-aromatic compounds, and to show the practical valueofmetal-freeC–Hfunctionalizationofaromatics. The chapter “Nucleophilic Substitution of Hydrogen in Arenes and Heteroarenes” by Mieczysław Ma˛kosza and Krzysztof Wojciechowski (Institute ofOrganicChemistry,ThePolishAcademyofSciences,Warsaw,Poland)provides uswiththecomprehensivereviewonbothoxidativeandeliminativeversionsofthe S H reactions, including the so-called vicarious nucleophilic substitution, which N appearstobeaveryessentialpartoftheS Hmethodology.Indeed,thepresenceof N a vicarious (auxiliary) group facilitates elimination of hydrogen with pair of electronsfromtheintermediatesH-adducts. The chapter “Direct Functionalization of C–H Fragments in Nitroarenes as a Synthetic Pathway to Condensed N-Heterocycles”, authored by Svyatoslav Shevelev and Alexey Starosotnikov (Zelinsky Institute of Organic Chemistry, Moscow, Russia), deals with the direct functionalization of C–H fragments in nitroarenes, followed by intramolecular cyclizations, as an effective synthetic pathwaytocondensednitrogenheterocycles. The chapter “C–H Functionalizations of Heteroaromatic N-Oxides”, prepared by Yoshinori Kondo (Tohoku University, Sendai, Japan), gives an excellent account of the recent advances in the field of nucleophilic C–H functionalization of heteroaromatic N-oxides, by using metal-free S H processes, as attractive N environmentallybenignmethodsoforganicsynthesis. Thechapter“TheS H-AminationofAromaticCompounds”,authoredbyAnna N Gulevskaya and Alexander Pozharsky (Rostov-on-Don University, Russia), presentsacomprehensivereviewonthedirectS Haminationofelectron-deficient N heteroaromaticcompounds.Recentadvancesinthisareaandmanynewaspectsof the S H amination are discussed, including new types of reagents, metal-free N catalysts, solvents and the hydride ion acceptors. The review shows that the S H N amination is rather promising synthetic alternative to both classic and transition metal-catalyzedamino-dehalogenationreactions. Finally, the chapter “Electrochemical C–H Functionalization of Arenes ” by IluminadaGallardoandGonzaloGuirado(UniversityofBarcelona,Spain)provide us with an excellent review showing a practical importance of electrochemical methods for the direct C–H functionalization of aromatic and heteroaromatic compounds– avery promising area thathas been advancedsignificantly by these authors. It is worth noting that three chapters of this volume have been written by the Russian chemists, and it seems to be a good opportunity to discuss the results Preface vii obtainedbytheseresearchgroupsandtoreflectproperlyaconsiderablebodyofthe dataontheS HreactionspublishedintheRussianchemicaljournals. N Webelievethatnumerousexamplesandmethodsforthedirectmetal-freeC–H functionalizationofarenesandheteroarenes,presentedbyaninternationalteamof chemistsinsixchaptersofthisvolume,arenotonlycomplementarytoeachother, butalsocreatethewholepictureoftheS Hreactions,enablingonetoestimatetheir N currentscope,syntheticpotentialandvalueas“chlorine-free”ecologicallybenign processes. In conclusion, we would like to express our sincere gratitude to all authors for theirvaluablecontributions.AlsowearethankfultoprofessorBertMaes(Univer- sity of Antwerp, Belgium), who encouraged us to prepare this volume, and Elizabeth Hawkins and Tanja Jaeger from Springer DE for their help and fruitful cooperation. Finally,weareverymuchobligedtoourfamiliesfortheirpatienceandunder- standingduringpreparationofthemanuscript. Ekaterinburg,Russia ValeryCharushinandOlegChupakhin 9December2013 Reference 1.ConstableDJCetal(2007)GreenChem9:41. . Contents Metal-FreeC–HFunctionalizationofAromaticCompounds ThroughtheActionofNucleophilicReagents. . . . . . . . . . . . . . . . . . . . 1 ValeryN.CharushinandOlegN.Chupakhin NucleophilicSubstitutionofHydrogeninArenesandHeteroarenes. . . 51 MieczysławMa˛koszaandKrzysztofWojciechowski DirectFunctionalizationofC–HFragmentsinNitroarenes asaSyntheticPathwaytoCondensedN-Heterocycles. . . . . . . . . . . . . . 107 SvyatoslavShevelevandAlexeyStarosotnikov C–HFunctionalizationofHeteroaromaticN-Oxides. . . . . . . . . . . . . . . 155 YoshinoriKondo TheSH-AminationofHeteroaromaticCompounds. . . . . . . . . . . . . . . . 179 N AnnaV.GulevskayaandAlexanderF.Pozharskii ElectrochemicalC–HFunctionalizationofArenesandHeteroarenes. . . 241 IluminadaGallardoandGonzaloGuirado Index. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 277 ix

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The series Topics in Heterocyclic Chemistry presents critical reviews on present and future trends in the research of heterocyclic compounds. Overall the scope is to cover topics dealing with all areas within heterocyclic chemistry, both experimental and theoretical, of interest to the general heter
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