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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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