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    Simmons-Smith Reaction - Wikipedia, The Free Encyclopedia

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    The Simmons-Smith reaction is an organic reaction that forms cyclopropane rings. It involves reacting an alkene with a methylene carbene generated from diiodomethane and an organozinc reagent. This reaction preserves the configuration of the original alkene double bond and occurs stereospecifically. The Simmons-Smith reaction is generally preferred for cyclopropanation but modifications have been developed to use cheaper reagents. An asymmetric version of the reaction was introduced in 1992 using a chiral ligand to induce enantioselectivity.

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    Simmons-Smith Reaction - Wikipedia, The Free Encyclopedia

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    The Simmons-Smith reaction is an organic reaction that forms cyclopropane rings. It involves reacting an alkene with a methylene carbene generated from diiodomethane and an organozinc reagent. This reaction preserves the configuration of the original alkene double bond and occurs stereospecifically. The Simmons-Smith reaction is generally preferred for cyclopropanation but modifications have been developed to use cheaper reagents. An asymmetric version of the reaction was introduced in 1992 using a chiral ligand to induce enantioselectivity.

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    Simmons–Smith Reaction

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    Simmons–Smith Reaction - Wikipedia, The Free Encyclopedia

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    The Simmons-Smith reaction is an organic reaction that forms cyclopropane rings. It involves reacting an alkene with a methylene carbene generated from diiodomethane and an organozinc reagent. This reaction preserves the configuration of the original alkene double bond and occurs stereospecifically. The Simmons-Smith reaction is generally preferred for cyclopropanation but modifications have been developed to use cheaper reagents. An asymmetric version of the reaction was introduced in 1992 using a chiral ligand to induce enantioselectivity.

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    © All Rights Reserved
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    112 views4 pages

    Simmons-Smith Reaction - Wikipedia, The Free Encyclopedia

    Uploaded by

    bhawanisr
    The Simmons-Smith reaction is an organic reaction that forms cyclopropane rings. It involves reacting an alkene with a methylene carbene generated from diiodomethane and an organozinc reagent. This reaction preserves the configuration of the original alkene double bond and occurs stereospecifically. The Simmons-Smith reaction is generally preferred for cyclopropanation but modifications have been developed to use cheaper reagents. An asymmetric version of the reaction was introduced in 1992 using a chiral ligand to induce enantioselectivity.

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    SimmonsSmithreactionWikipedia,thefreeencyclopedia

    SimmonsSmithreaction
    FromWikipedia,thefreeencyclopedia

    TheSimmonsSmithreactionisanorganiccheletropicreaction
    involvinganorganozinccarbenoidthatreactswithanalkene(or
    alkyne)toformacyclopropane.[1][2][3]ItisnamedafterHoward
    EnsignSimmons,Jr.andRonaldD.Smith.Itusesamethylene
    freeradicalintermediatethatisdeliveredtobothcarbonsofthe
    alkenesimultaneously,thereforetheconfigurationofthedouble
    bondispreservedintheproductandthereactionis
    stereospecific.[4]

    SimmonsSmithreaction

    SimmonsSmithreactioninprogress
    SimmonsSmithreaction
    Namedafter

    HowardEnsign
    Simmons,Jr.
    RonaldD.Smith

    Reactiontype

    Ringformingreaction
    Identifiers

    Organic
    simmonssmithreaction
    ChemistryPortal
    RSContologyID RXNO:0000258

    Thus,cyclohexene,diiodomethane,andazinccoppercouple(asiodomethylzinciodide,ICH2ZnI)yieldnorcarane
    (bicyclo[4.1.0]heptane).[5][6]

    TheSimmonsSmithreactionisgenerallypreferredoverothermethodsofcyclopropanation,[7]howeveritcanbe
    expensiveduetothehighcostofdiiodomethane.Modificationsinvolvingcheaperalternativeshavebeen
    developed,suchasdibromomethane[8]ordiazomethaneandzinciodide.[9]Thereactivityofthesystemcanalsobe
    increasedbyexchangingthezinccoppercouplefordiethylzinc,[10]howeverasthisreagentispyrophoricitmust
    behandledcarefully.
    TheSimmonsSmithreactionisgenerallysubjecttostericeffects,andthuscyclopropanationusuallytakesplace
    onthelesshinderedface.[11][12]However,whenahydroxysubstituentispresentinthesubstrateinproximitytothe
    doublebond,thezinccoordinateswiththehydroxysubstituent,directingcyclopropanationcistothehydroxyl
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    group(whichmaynotcorrespondtocyclopropanationofthestericallymostaccessiblefaceofthedouble
    bond):[13]Aninteractive3Dmodelofthisreactioncanbeseenhere(http://www.chemtube3d.com/Cyclopropanatio
    n.html)(javarequired).

    TheSimmonsSmithreagent,namelydiiodomethaneanddiethylzinc,canreactwithallylicthioetherstogenerate
    sulfurylides,whichcansubsequentlyundergoa2,3sigmatropicrearrangement,andwillnotcyclopropanatean
    alkeneinthesamemoleculeunlessexcessSimmonsSmithreagentisused:[14]

    AsymmetricSimmonsSmithreaction
    Althoughasymmetriccyclopropanationmethodsbasedondiazocompounds(seebisoxazolineligand)existsince
    1966,theasymmetricSimmonsSmithreactionwasintroducedin1992[15]withareactionofcinnamylalcohol
    withdiethylzinc,diiodomethaneandachiraldisulfonamideindichloromethane:

    Thehydroxylgroupisaprerequisiteservingasananchorforzinc.Aninteractive3Dmodelofasimilarreaction[16]
    canbeseenhere(http://www.chemtube3d.com/AsymCat_Simmons_Smith.html)(javarequired).Inanother
    versionofthisreactiontheligandisbasedonsalenandLewisacidDIBALisadded:[17]

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    References
    1.HowardEnsignSimmons,Jr.Smith,R.D.(1958)."ANewSynthesisofCyclopropanesfromOlefins".J.Am.Chem.
    Soc.80:5323.doi:10.1021/ja01552a080.
    2.Simmons,H.E.Smith,R.D.(1959)."ANewSynthesisofCyclopropanes".J.Am.Chem.Soc.81:4256.
    doi:10.1021/ja01525a036.
    3.Denis,J.M.Girard,J.M.Conia,J.M(1972)."ImprovedSimmonsSmithReactions".Synthesis1972:549.
    doi:10.1055/s197221919.
    4.Charette,A.B.Beauchemin,A.Org.React.2001,58,1.doi:10.1002/0471264180.or058.01(https://dx.doi.org/10.100
    2%2F0471264180.or058.01)
    5.Smith,R.D.Simmons,H.E."Norcarane".Org.Synth.Coll.Vol.5,p.855
    6.Ito,Y.Fujii,S.Nakatuska,M.Kawamoto,F.Saegusa,T.(1988)."OneCarbonRingExpansionOfCycloalkanonesTo
    ConjugatedCycloalkenones:2Cyclohepten1one".Org.Synth.Coll.Vol.6,p.327
    7.Clayden,JonathanGreeves,NickWarren,StuartWothers,Peter(2001).OrganicChemistry(1sted.).Oxford
    UniversityPress.ISBN9780198503460.Page1067
    8.Fabisch,BodoMitchell,TerenceN.(1984)."AninexpensivemodificationoftheSimmonsSmithreaction:The
    formationofbromomethylzincbromideasstudiedbyNMRspectroscopy".JournalofOrganometallicChemistry269(3):
    219221.doi:10.1016/0022328X(84)803058.
    9.Wittig,GeorgWingler,Frank(1August1964)."bermethylenierteMetallhalogenide,IV.CyclopropanBildungaus
    OlefinenmitBishalogenmethylzink".ChemischeBerichte97(8):21462164.doi:10.1002/cber.19640970808.
    10.Furukawa,J.Kawabata,N.Nishimura,J.(1968)."Synthesisofcyclopropanesbythereactionofolefinswithdialkylzinc
    andmethyleneiodide".Tetrahedron24(1):5358.doi:10.1016/00404020(68)890076.
    11.Simmons,H.E.etal.(1973).Org.React.(Review)20:1.Missingorempty|title=(help)
    12.Girard,C.Conia,J.M.(1978).J.Chem.Res.(S)(Review):182.Missingorempty|title=(help)
    13.PaulA.Grieco,TomeiOguri,ChiaLinJ.Wang,andEricWilliams(1977)."Stereochemistryandtotalsynthesisof()
    ivangulin".J.Org.Chem42:4113.doi:10.1021/jo00445a027.
    14.Cohen,T.Kosarych,Z.(1982)."CompleteregioandstereospecificityintheLewisacidcatalyzedDielsAlderreactions
    of(Z)2methoxy1(phenylthio)1,3butadienes.ConversionoftheCSconfigurationofanadducttotheCC
    configurationattheallylicpositionbya[2,3]sigmatropicrearrangement".J.Org.Chem47:4005.
    doi:10.1021/jo00141a047.
    15.HideyoTakahashi,MasatoYoshioka,MasajiOhnoandSusumuKobayashi(1992)."Acatalyticenantioselectivereaction
    usingaC2symmetricdisulfonamideasachiralligand:cyclopropanationofallylicalcoholsbytheEt2ZnCH2I2
    disulfonamidesystem".TetrahedronLetters33(18):25752578.doi:10.1016/S00404039(00)922469.
    16.Wang,TaoLiang,YongYu,ZhiXiang(2011)."DensityFunctionalTheoryStudyoftheMechanismandOriginsof
    StereoselectivityintheAsymmetricSimmonsSmithCyclopropanationwithCharetteChiralDioxaborolaneLigand".
    JournaloftheAmericanChemicalSociety133(24):93439353.doi:10.1021/ja111330z.
    17.HiroakiShitamaandTsutomuKatsuki(2008)."AsymmetricSimmonsSmithReactionofAllylicAlcoholswithAlLewis
    Acid/NLewisBaseBifunctionalAl(Salalen)Catalyst".Angew.Chem.Int.Ed.47:2450.doi:10.1002/anie.200705641.

    Externallinks
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    SimmonsSmithreactionatOrganicChemistryPortal(http://www.organicchemistry.org/namedreactions/si
    mmonssmithreaction.shtm)
    Retrievedfrom"https://en.wikipedia.org/w/index.php?title=Simmons
    Smith_reaction&oldid=688083605"

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    Smithreaction.

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    Namereactions Cyclopropanes Cheletropicreactions
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