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  • Arndt Eistert Synthesis

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    Sreedevi Krishnakumar
    47 Ansichten2 Seiten
    The Arndt-Eistert Synthesis allows the formation of homologated carboxylic acids or their derivatives through a one-carbon homologation reaction. It involves the reaction of activated carboxylic acids with diazomethane to form α-diazoketones, which then undergo Wolff rearrangement in the presence of nucleophiles like water or alcohols to form ketenes. These ketenes react with the nucleophiles to yield the homologated carboxylic acids or esters. The method is widely used to synthesize β-amino acids for potential pharmaceutical applications.

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    The Arndt-Eistert Synthesis allows the formation of homologated carboxylic acids or their derivatives through a one-carbon homologation reaction. It involves the reaction of activated carboxylic acids with diazomethane to form α-diazoketones, which then undergo Wolff rearrangement in the presence of nucleophiles like water or alcohols to form ketenes. These ketenes react with the nucleophiles to yield the homologated carboxylic acids or esters. The method is widely used to synthesize β-amino acids for potential pharmaceutical applications.

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    47 Ansichten2 Seiten

    Arndt Eistert Synthesis

    Hochgeladen von

    Sreedevi Krishnakumar
    The Arndt-Eistert Synthesis allows the formation of homologated carboxylic acids or their derivatives through a one-carbon homologation reaction. It involves the reaction of activated carboxylic acids with diazomethane to form α-diazoketones, which then undergo Wolff rearrangement in the presence of nucleophiles like water or alcohols to form ketenes. These ketenes react with the nucleophiles to yield the homologated carboxylic acids or esters. The method is widely used to synthesize β-amino acids for potential pharmaceutical applications.

    Copyright:

    © All Rights Reserved
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    Markieren Sie unangemessene Inhalte
    von 2

    10/16/2015

    ArndtEistertSynthesis

    OrganicChemistryPortal
    Reactions>>NameReactions
    FurtherInformation
    Literature
    RelatedReactions
    WolffRearrangement
    Homologations
    Synthesisofcarboxylicacids
    SynthesisofDiazoketones

    ArndtEistertSynthesis

    TheArndtEistertSynthesisallowstheformationofhomologatedcarboxylicacidsortheirderivativesbyreactionoftheactivatedcarboxylicacidswithdiazomethane
    andsubsequentWolffRearrangementoftheintermediatediazoketonesinthepresenceofnucleophilessuchaswater,alcohols,oramines.
    MechanismoftheArndtEistertSynthesis
    Inthefirststepofthisonecarbonhomologation,thediazomethanecarbonisacylatedbyanacidchlorideormixedanhydride,togiveandiazoketone.Theexcess
    diazomethanecanbedestroyedbyadditionofsmallamountsofaceticacidorvigorousstirring.Mostdiazoketonesarestableandcanbeisolatedandpurifiedby
    columnchromatography(seerecentliteratureforspecificmethods).

    ThekeystepoftheArndtEistertHomologationistheWolffRearrangementofthediazoketonestoketenes,whichcanbeaccomplishedthermally(overtherange
    betweenr.t.and750C[Zeller,Angew.Chem.Int.Ed.,1975,14,32.DOI]),photochemicallyorbysilver(I)catalysis.Thereactionisconductedinthepresenceof
    nucleophilessuchaswater(toyieldcarboxylicacids),alcohols(togiveesters)oramines(togiveamides),tocapturetheketeneintermediateandavoidthecompeting
    formationofdiketenes.

    Themethodiswidelyusednowadaysforthesynthesisofaminoacids.Peptidesthatcontainaminoacidsfeaturealowerrateofmetabolicdegradationandare
    thereforeofinterestforpharmaceuticalapplications.

    http://www.organicchemistry.org/namedreactions/arndteistertsynthesis.shtm

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    ArndtEistertSynthesis

    RecentLiterature

    SynthesisofFmocHomoaminoAcidsbyUltrasoundPromotedWolffRearrangement
    A.Mller,C.Vogt,N.Sewald,Synthesis,1998,837841.

    TheArndtEistertReactioninPeptideChemistry:AFacileAccesstoHomopeptides
    J.Podlech,D.Seebach,Angew.Chem.Int.Ed.,1995,34,471472.

    ImprovedArndtEistertSynthesisofDiazoketonesRequiringMinimalDiazomethaneinthePresenceofCalciumOxideasAcidScavenger
    V.Pace,G.Verniest,J.V.Sinisterra,A.R.Alcntara,N.DeKimpe,J.Org.Chem.,2010,75,57605763.

    Trimethylsilyldiazomethaneinthepreparationofdiazoketonesviamixedanhydrideandcouplingreagentmethods:anewapproachtotheArndtEistertsynthesis
    J.Cesar,M.SollnerDolenc,TetrahedronLett.,2001,42,70997102.

    http://www.organicchemistry.org/namedreactions/arndteistertsynthesis.shtm

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