Isocyanide Chemistry: Applications in Synthesis and Material Science

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Wiley-VCH Verlag GmbH & Co. KGaA, 2012. — 587 p.The efficacy of isocyanide reactions in the synthesis of natural or naturallike products has resulted in a renaissance of isocyanide chemistry. Now isocyanides are widely used in different branches of organic, inorganic, coordination, combinatorial and medicinal chemistryThis invaluable reference is the only book to cover the topic in such depth, presenting all aspects of synthetic isonitrile chemistry. The highlyexperienced and internationally renowned editor has brought together an equally distinguished team of authors who cover multicomponentreactions, isonitriles in total synthesis, isonitriles in polymer chemistry and much more.ContentsChiral Nonracemic IsocyanidesIntroductionSimple Unfunctionalized IsocyanidesIsocyanides Containing Carboxylic, Sulfonyl, or Phosphonyl Groupsα-Isocyano Estersα-Isocyano AmidesOther Isocyano Esters or AmidesChiral Sulfonylmethyl or Phosphonylmethyl IsocyanidesIsocyanides Containing Amino or Alcoholic FunctionalitiesChiral Amino or Azido IsocyanidesChiral Hydroxy IsocyanidesNatural IsocyanidesIsolation and Natural SourcesSynthesis of Naturally Occurring IsocyanidesIsocyanides Used in the Synthesis of Chiral PolyisocyanidesPropertiesSynthesisApplicationsReferencesGeneral Aspects of Isocyanide ReactivityIntroductionIsocyanide–Cyanide RearrangementOxidation/Reduction of the Isocyano GroupOxidation of the Isocyano GroupReactions with Sulfur and SeleniumReduction of the Isocyano GroupReactions of Isocyanides with ElectrophilesReaction with AcidsReactions with Halogens and Acyl HalidesReactions with Activated Alkenes and AlkynesReactions with Carbonyl Compounds and IminesReactions with Activated HeterocumulensReactions of Isocyanides with NucleophilesReactions with Organometallic CompoundsReactions with Hydroxide, Alcohols, and AminesConclusionsReferencesα-Acidic Isocyanides in Multicomponent ChemistryIntroductionSynthesis of α-Acidic IsocyanidesReactivity of α-Acidic IsocyanidesMCRs Involving α-Acidic Isocyanidesvan Leusen Imidazole MCR2,6,7-Trisubstituted Quinoxaline MCR4,5-Disubstituted Oxazole MCRNitropyrrole MCR2,4,5-Trisubstituted Oxazole MCR2,4,5-Trisubstituted OxazolesVariations on the 2,4,5-Trisubstituted Oxazole MCROxazole MCR and In-Situ Domino ProcessesImidazoline MCRImidazoline MCR in the Union of MCRsDihydropyridone MCRConclusionsReferencesSynthetic Application of Isocyanoacetic Acid DerivativesIntroductionSynthesis of α-Isocyanoacetate DerivativesAlkylation of Isocyanoacetic Acid Derivativesα-Isocyanoacetates as Michael DonorsReaction of Isocyanoacetic Acids with Alkynes: Synthesis of PyrrolesReaction of Isocyanoacetic Acid Derivatives with Carbonyl Compounds and IminesAldol-Type Reaction of Isocyanoacetic Acids with Aldehydes: Synthesis of OxazolinesContents VIITransition Metal-Catalyzed Aldol-Type ReactionsReaction of Isocyanoacetic Acids with Imines: Imidazoline FormationReaction with Acylating AgentsMulticomponent Reactions of Isocyanoacetic Acid DerivativesChemistry of Isocyanoacetates Bearing an Additional Functional GroupReactions of Isocyanoacetic Acids with Sulfur ElectrophilesMiscellaneous ReactionsConcluding RemarksNotes Added in ProofReferencesUgi and Passerini Reactions with Carboxylic Acid SurrogatesIntroductionCarboxylic Acid SurrogatesThiocarboxylic AcidsCarbonic Acid and DerivativesSelenide and Sulfi deSilanolIsocyanic Acid and DerivativesHydrazoic AcidPhenols and DerivativesCyanamideUse of Mineral and Lewis AcidsUgi and Passerini Reactions Triggered by Mineral AcidsUgi and Passerini Reactions Triggered by Lewis AcidsConclusionsReferencesAmine (Imine) Component Surrogates in the Ugi Reaction and Related Isocyanide-Based Multicomponent ReactionsIntroductionHydroxylamine Components in the Ugi ReactionHydrazine Components in the Ugi ReactionMiscellaneous Amine Surrogates for the Ugi ReactionActivated Azines in Reactions with IsocyanidesEnamines, Masked Imines, and Cyclic Imines in the Ugi ReactionConcluding RemarksAcknowledgmentsReferencesVIII ContentsMultiple Multicomponent Reactions with IsocyanidesLudger A. Wessjohann, Ricardo A.W. Neves Filho, and Daniel G. RiveraIntroductionOne-Pot Multiple IMCRsSynthesis of Multivalent GlycoconjugatesSynthesis of Hybrid Peptide–Peptoid PodandsCovalent Modifi cation and Immobilization of ProteinsAssembly of Polysaccharide Networks as Synthetic HydrogelsSynthesis of Macromolecules by Multicomponent PolymerizationIsocyanide-Based Multiple Multicomponent MacrocyclizationsSynthesis of Hybrid Macrocycles by Double Ugi-4CR-Based MacrocyclizationsSynthesis of Macrobicycles by Threefold Ugi-4CR-Based MacrocyclizationSequential Isocyanide-Based MCRsSequential Approaches to Linear and Branched ScaffoldsSequential Approaches to MacrocyclesConvergent Approach to Natural Product MimicsConclusionsReferencesZwitterions and Zwitterion-Trapping Agents in Isocyanide ChemistryIntroductionGeneration of Zwitterionic Species by the Addition of Isocyanides to AlkynesCH-Acids as Zwitterion-Trapping AgentsNH-Acids as Zwitterion-Trapping AgentsOH-Acids as Zwitterion-Trapping AgentsCarbonyl Compounds as Zwitterion-Trapping AgentsImine Compounds as Zwitterion-Trapping AgentsElectron-Defi cient Olefi ns as Zwitterion-Trapping AgentsMiscellaneous Compounds as Zwitterion-Trapping AgentsGeneration of Zwitterionic Species by the Addition of Isocyanides to ArynesGeneration of Zwitterionic Species by the Addition of Isocyanides toElectron-Defi cient Olefi nsMiscellaneous Reports for the Generation of Zwitterionic SpeciesIsocyanides as Zwitterion-Trapping AgentsConclusionsAcknowledgmentsReferencesContents IXRecent Progress in Nonclassical Isocyanide-Based MCRsIntroductionType I MCRs: Isocyanide Attack on Activated SpeciesType II MCRs: Isocyanide ActivationType III MCRs: Formal Isocyanide Insertion ProcessesConclusionsAcknowledgmentsReferencesApplications of Isocyanides in IMCRs for the Rapid Generation of Molecular DiversityIntroductionUgi/Deprotect/Cyclize (UDC) MethodologyUgi-4CC: One Internal NucleophileTMSN3-Modifi ed Ugi-4CC: One Internal NucleophileUgi-4CC: Two Internal NucleophilesUgi-4CC: Three Internal NucleophilesUgi-5CC: One Internal NucleophileSecondary Reactions of Ugi ProductsNucleophilic Additions and SubstitutionsAlkylationsMitsunobu ReactionsLactonization and LactamizationBase- or Acid-Promoted CondensationsNucleophilic Aromatic SubstitutionsPalladium-Mediated ReactionsRing-Closing MetathesesStaudinger–aza-Wittig ReactionsCycloadditionsThe Bifunctional Approach (BIFA)Applications of Amino AcidsApplications of Cyclic IminesApplications of Tethered Aldehyde and Keto AcidsHeterocyclic Amidines as a Tethered Ugi InputCombined Bifunctional and Post-Condensation Modifi cationsAcknowledgmentsAbbreviationsReferencesX ContentsSynthesis of Pyrroles and Their Derivatives from IsocyanidesIntroductionSynthesis of Pyrroles Using TosMICSynthesis of Pyrroles Using IsocyanoacetatesSynthesis from NitroalkenesSynthesis from α,β-Unsaturated SulfonesSynthesis from AlkynesSynthesis from Aromatic Nitro Compounds: Isoindole DerivativesSynthesis of Porphyrins and Related CompoundsTetramerizationMeso-Tetraarylporphyrins via the Lindsey Procedure[3+2] and [2+2] MethodsExpanded, Contracted, and Isomeric PorphyrinsFunctional Dyes from PyrrolesConclusionReferencesIsocyanide-Based Multicomponent Reactions towardsBenzodiazepinesIntroduction1,4-Benzodiazepine Scaffolds Assembled via IMCR ChemistryTwo-Ring SystemsFused-Ring Systems1,5-Benzodiazepine Scaffolds Assembled via IMCR ChemistryOutlookReferencesApplications of Isocyanides in the Synthesis of HeterocyclesIntroductionFuransPyrrolesOxazolesIsoxazolesThiazolesImidazolesPyrazolesOxadiazoles and TriazolesTetrazolesBenzofurans and BenzimidazolesIndolesQuinolinesQuinoxalineAbbreviationsReferencesRenaissance of Isocyanoarenes as Ligands in Low-Valent OrganometallicsHistorical PerspectiveIsocyanidemetalates and Related Low-Valent ComplexesIntroductionFour-Coordinate Isocyanidemetalates and Redox-Related ComplexesFive-Coordinate IsocyanidemetalatesSix-Coordinate Isocyanidemetalates and Redox-Related ComplexesCoordination and Surface Chemistry of Nonbenzenoid IsocyanoarenesIsocyanoazulenesOrganometallic η5 -IsocyanocyclopentadienidesHomoleptic Complexes of Nonbenzenoid IsocyanoarenesBridging Nonbenzenoid IsocyanoarenesSelf-Assembled Monolayer Films of Nonbenzenoid Isocyano- and Diisocyanoarenes on Gold SurfacesConclusions and OutlookAcknowledgmentsReferencesCarbene Complexes Derived from Metal-Bound Isocyanides: Recent AdvancesIntroductionCoupling of the Isocyanide Ligand with Simple Amines or AlcoholsCoupling of the Isocyanide Ligand with Functionalized Amines or AlcoholsCoupling of the Isocyanide Ligand with a Hydrazine or HydrazoneCoupling of the Isocyanide Ligand with an Imine or AmidineIntramolecular Cyclizations of Functionalized Isocyanide LigandsCoupling of Isocyanides with DipolesOther ReactionsFinal RemarksAcknowledgmentsReferencesXII ContentsPolyisocyanidesNiels Akeroyd, Roeland J.M. Nolte, and Alan E. RowanIntroductionChiral PolymersPolyisocyanides and Their MonomersThe Polymerization MechanismConformation of the Polymeric BackbonePolyisocyanopeptidesPolyisocyanides as Scaffolds for the Anchoring of Chromophoric MoleculesFunctional PolyisocyanidesConclusions and OutlookReferences