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ConjugatedDienes

ConjugatedDienes

A.Definition
Aconjugatedsystemreferstoasystemofpielectronswhichconsistsofthreeormore2pzAOsondirectlyconnectedatoms.TheresultingpiMOsare
thendelocalizedoverthreeormoreatoms.
Aconjugateddieneisamoleculewhichcontainstwoalkenelinkageswhichareinconjugation,givingafouratom(also4AO)delocalizedsystem.
Simpleexampleofaconjugatedsystemis1,3butadiene,inwhichthetwopibondsaredirectlyconnectedsoastoallowcontinuousoverlapoverthe
entiresystemoffourcarbonatoms.

Dieneswhicharenotconjugateddienesareexemplifiedby1,2propadiene(allene)and1,5pentadiene.Inthelatter,thetwoalkenelinkagesare

separatedbyasaturatedcarbonatom,sothatthepioverlapisnotcontinuous.Intheformer,thetwopibondsareperpendicularanddonotinteractor
delocalize.But1,3pentadieneisaconjugatediene.

Nomenclature.Thesuffixdieneisusedtodescribeamoleculehavingtwoenelinkages.Asinglenumberisusedtodesignatethestartingpositionofeach
doublebond,e.g.asshownbelow.Notethatwhennamingasubstanceasadiene,thenumberingsystemoftheparentchainbeginsattheendofthechaincloses
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tooneofthedoublebonds.

4methyl1,3pentadiene
ConformationsofConjugatedDienes.
InordertohaveaconjugatedsystemofAOs,inwhichallofthe2pAOsareparallel(e.g.,all2pz),all4ofthecarbonsofthedienesystemmustbe
coplanar,aswewillseefurtherinamoment.
Thismeansthatthereareonlytwogroundstateconformationsofsuchaconjugateddiene.Oneiscalledstransandtheotherscis.
Thecisortransdesignationisbasedupontherelationshiparoundthecentral,formallysingleCCbond.

Thestransconformationismorethermodynamicallystablebecausethescisconformationhasastericrepulsionbetweenthetwoinsidehydrogens.
However,bothconformationsarefoundatleasttosomeextent.Wewillseethatalthoughthestransconformationispreponderant,thescis
conformationisextremelyimportantinsomereactions.

Itshouldalsobenotedthatinsomecyclicsystems,thisinsiderepulsionisnotpresent,andthemoleculeisrigidlycompelledtohavethescis
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conformation(nootherstableconformationexists).Inothercycliccases,thestransconformationmaybetheonlyoneavailablei.e.,thereis0%scis.

3.[2pts]Usingtheabovedrawings,explainwhytheseplanarconformationsarestronglyfavoredoverother,nonplanar,conformations.Showany
relevantoverlapsbymeansoforbitaldepictions.
Onlyintheplanarconformationsarethe2pAOsatC2andC3parallel,soastogivemaximumoverlapandresonancestabilization.(Seedrawing
abovefororbitaloverlaps)
4.[1pts]Nameonetypeofeffectwouldnormallytendtodisfavortheplanarforms.Torsionaleffects.
5.[1pts]Whichoneofthetwoplanarformsisthemorestable?Explain,usingastructuralillustration.Thestransconformationisthemorestableone
becauseoftheinsideH/Hstericrepulsioninthescisconformation.

Notethatoneorbothoftheenelinkagesmayhavethecapabilityofexistingaseitherthecisortransisomer.Insuchacase,thelocantmustbepreceded

byacisortransorE/Zspecification.
WhenaterminalcarbonoftheconjugatedsystemhasacisorZsubstituent(anythingotherthanH),thescisconformationisessentiallyunpopulated,

becauseitistoohighinenergy.

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Inbothcasesshownabove,thestransconformationispredominant,butinthefirstcaseitistheexclusiveconformer.

ResonanceStabilizationofConjugatedDienes
Sincethefourelectronsofthetwodoublebondsaredelocalizedoverafouratomconjugatedsystem,wewouldexpectthatthispisystemismorestable
thanthesumoftwoalkenedoublebonds.Thisisthecase,althoughthestabilizationisrelativelysmall(perhapslessthan8kcal/mol)becausethesecond
resonancestructureisrelativelyhigherinenergythanthefirstone(onelessbondchargeseparation).

odihedralangleshown

Nevertheless,thisresonancemakesitrelativelydifficulttorotatearoundthecentral(C2C3)doublebond,becauseatthe90

below,alltracesofresonancestabilizationarelost,andthedienelinkagesareindependent(notconjugated).Rotationoccurs,butrequiresabout8
kcal/mol,alargerenergythanrequiredforrotationaroundtypicalCCsinglebonds.

ConjugateAdditiontoDienes.WearefamiliarwiththecircumstancethatHXaddstoalkenestogivealkylhalides.Itwould,ofcourse,notbesurprisingifa
similarreactionoccurswithconjugateddienes.Themechanismofthiselectrophilicadditionreactionisshownbelow:

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Interestingly,twoproductsareformed,inoneofwhichHBrhasineffectaddedtothe1and4positions(theterminalpositions)ofthediene,withbothof

theoriginaldoublebondsbeingbrokenandreplacedbyonewhichhasshiftedtothecentralcarbonsoftheoriginaldiene.Thisisthefirstproductshown
above:trans4bromo2butene(alsothecisisomerisformedinsmallamounts).
IneffecttheprotonhasaddedtoC1andthebromideiontotheC4position.Thiskindofproductissaidtoderivefromconjugateadditiontothediene.
Intheotherproduct(3bromo1butene),aprotonhasaddedtoC1andabromideiontoC2.Thisisamoreorlessnormal1,2additiontoanalkene
doublebond.Theotherdoublebondremainsunaffected.
Theformationoftwoproductsistheresultofthecircumstancethattheintermediatecarbocation(generically,anallylictypecarbocation)isaconjugated
systeminwhichtheelectronsaredelocalizedover3atoms,andthepositivechargeoverthetwoterminalatomsoftheallylicconjugatedsystem.
Thenucleophilecanreactateithersiteofpositivecharge,givingoneortheotherofthetwoproducts.

AllylicResonanceStabilization.Allylicresonancestabilizationislarge,becauseintheparentallylcationtherearetwoequivalentresonancestructures.In
otherderivativesoftheallylcarbocation,thestructuresmaynotbeexactlyequalinenergybutarecloseenoughtogivesimilarlylargeresonancestabilizations.
Intheparentallylcation,thereisahalfunitofpositivechargeonC1andalsothesameamountonC3,butnoneonC2.Wecansaythatthereisextensive
carbocationcharacteratbothoftheseterminalcarbons,soanucleophilecanreactequallyreadilyateitherposition(butnotatC2).

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UnsymmetricalAllylicCarbocations
Inthecaseofanunsymmetricalallyliccarbocation,thetworesonancestructuresarenotequalinenergy,andtherealstructure,whileintermediate,will
morecloselyresemblethestructureoflowerenergy.
Intheadditionto1,3butadiene,suchanunsymmetricalallyliccationisformed.

ResonanceTheoreticalTreatment

DottedLine/PartialChargeStructure

Thefirststructuredrawnaboveisoflowerenergythanthesecondcanonicalstructure,becausethefirstisasecondarycarbocationcanonicalstructure,
whilethesecondisaprimarycarbocationcanonicalstructure.

Therealstructure(resonancehybride)morecloselyresemblesthelowerenergystructure,whichhasasecondarycarbocationcenter.

Therefore,theresonancehybridhasmorecarbocationcharacteratthesecondarythanattheprimarycarbon.
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Thebromideionthereforereactspreferentially(morerapidly)atthesiteofhigherpositivechargedensity.Thatis,atthesecondarycarbon,togive:

However,theratesofreactionatthetwositesarenottoodifferent,sothatthesecondproductisalsoformedincompetitionwiththeaboveproduct,by

reactionattheprimarycarbon.Thisproductistheconjugateadditionproduct.

Thisiskineticcontrol(or,ratecontrol).Thetwoproductsareformedin80%and#0%amountswhenthereactioniscarriedoutatlowtemperature.

Undertheseconditions,theproducts,onceformed,donotequilibratewitheachother,sothattheobservedproductmixturerepresentstheratioinwhich
theywereoriginallyformed.

AdditionofHBrto1,3ButadieneatRoomTemperature:ThermodynamicControl
Whentheverysamereactioniscarriedoutatroomtemperature,thesameproductsareformed,buttheproductratioissignificantlychanged.Underthese
conditions,theconjugateadditionproduct(shownbelow)isthemajorproduct(about80%)andthe1,2additionproductistheminorproduct(about
20%).

Itisnotbecausethereactionofbromideionwiththeallyliccarbocationhassuddenlychangeditspreferenceforreactingatthesecondarysite,but

becauseatroomtemperaturethesetwoproductsareequilibratingtogivethethermodynamicallymorestableproductinexcess.
Thereasontheconjugate(1,4)additionproductisthermodynamicallymorestableisthatithasadisubstitutedalkenemoiety,whilethe1,2addition

productisonlymonosubstituted.
Themechanismbywhichthetwobromidesequilibrateisgivenbelowandsimplyinvolvesthereformationoftheallyliccarbocation/bromideionpair.

Thermodynamicvs.KineticControl:Testing
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Supposetwoproducts,AandB,areformedinacertainreactionandproductAisthemajorproduct.Youwanttoknowwhetherthisproductmixtureis
kineticallycontrolledorthermodynamicallycontrolled.Howcouldyoutestwhethertheproductmixtureiskineticallycontrolled(thereforerequiringananalysis
intermsofCompetingTransitionStatestoexplainthepreferenceforoneproductortheother)orthermodynamicallycontrolled(therebyrequiringananalysis
oftherelativestabilitiesofthetwoproducts).

Wecould,e.g.,obtainpuresamplesofAandB.
Subjecteachindividuallypureisomertotheexactreactionconditions,includingtemperature,solvent,reactiontime,etc.
IfAremainspureA,withoutisomerizing,andBremainspureB,afterthisreactiontime,theproductmixturewaskineticallycontrolled.Essentially,this
experimentshowsthatbothproductsarestableunderthereactionconditions,onceformed,anddonotrearrangeintotheother.
Onthetherhand,ifpureAandpureBbothrearrangetothesamemixtureofAandBasobtainedintheoriginalreaction,theproductmixtureis
thermodynamicallycontrolled.

DielsAlderCycloaddition
OneofthemostusefulreactionsinsyntheticorganicchemistryistheDielsAlderreaction,whichconsistsofthereactionofaconjugateddiene
(specificallyinitsscisconformation)withanalkene(preferablyanelectrondeficientalkene).

TheDielsAlderreactionisespeciallyimportantinorganicsynthesisfortwomainreasons.First,itaccomplishestheformationoftwocarboncarbon
bonds.Secondly,itenablesonetoconstructacyclic,sixmemberedringsystem.Bothoftheseaspectsallowonetoaccomplishadramaticincreasein
molecularcomplexityforthepurposeofsynthesizingcomplexmolecules.
Considertheprototype(simplest)DielsAldercycloadditionreactionbetween1,3butadieneandethane,shownbelow.

ThisreactioninvolvesbreakingthreepibondsandformingonenewpibondplustwonewsigmaCCbonds.Thereisanetconversionof2pibondsto

twosigmabonds,sothisishighlyfavorable.
Recallthatconvertingtwomoleculesintooneisentropicallyunfavorable,butthelargeenthalpicpreferenceforsigmabondsisdominant.
InthecontextofaDielsAlderreaction,thealkeneisreferredtoasthedienophile.
Thereactionmechanismisaconcertedone,withallbondsbeingmadeandbrokeninaconcertedway.
TheTSmodelforthisreactionisdevelopedbelow,usingresonancetheory,andRandPlikestructures.

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Characterization:TheTShasacyclic6econjugatedsystem.Fourpielectronscomefromtheconjugateddienesystemandtwofromthealkenepibond.
Since6ecyclicconjugatedsystemsareespeciallyfavorable(HuckelRule),thisisarelativelyfavorableTS.[Notthatisisanenergyminimum,butthe

energymaximumisloweredconsiderablybythestabilityofthepielectronsystem.
SuchtransitionstatescanbecalledaromaticTSs.
Notethat,sinceethenemustbondsimultaneouslytoCarbons1and4ofthediene,thescisconformationofthedieneisabsolutelyrequired.The

terminalatomsofthestransconformeraremuchtwofaraparttobebridgedbyasingleetheneunit.Althoughtheequilibriummixturecontainsonly
abut2%ofthecisconformer,theequilibriumisreestablishedrapidly,sothatthesupplyoftheneededconformeriscontinuouslyandrapidlybeing
restored.
Anydienewhichcannotadoptthescisconformationforsomereason(aswehavepreviouslynoted),cannotundergotheDielsAlderreaction.Dienes
whichexistonlyinthecisconformationareespeciallyaptatundergoingtheDielsAlderreaction.
AmorerepresentativeAOmodelofthecyclicTSisgivenbelow:

HypotheticalReactionsWhichWouldHavetoOccurviaanAntiaromaticTS.
ThereactionbetweentwoetheneunitstogiveacyclobutaneisthermodynamicallymoredifficultthantheDielsAlderreactionbecauseoftheringstrain
presentinthefourmemberedring.
However,itisalsomuch,muchlessfavorablekineticallybecausetheTSisacyclicsystemof4electrons,whichisespeciallyunfavorable.SuchTSscan
becalledantiaromaticTSs.
Althoughexamplesofsuchreactionsareknown,theytypicallyrequirepowerfullyforcingconditionsand,importantly,whentheyareforcedtooccur
theydonotoccurviaaconcertedpathway,sothattheyavoidtheunstable4esystem.[Onebondisformedatatime,inaradicalmechanism]

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DielsAlderReactionswithElectronDeficientDienophiles.
Forreasonswhichwewillnotdelveinto,etheneitselfandothersimplealkenesarenotthebestdienophilesforDielsAlderreactions.However,alkenes
whichhaveelectronwithdrawingsubstituentsaremuchbetter.Theyreactundermuchmilderconditions(sometimesatRT)andinbetteryield.Esterfunctions
areamongthosewhichstronglyacceleratetheDielsAlderreaction.

Theequationbelowillustratesthereactionsofapaircis/transisomerscontainingtwoesterfunctionsinthedienophilewithanespeciallyreactivecyclic
diene,whichexistsexclusivelyinthescisconformation.Thetransisomerofthedienophileiscalleddimethylfumaratethecisisomerisdimethyl
maleate.

Weespeciallywanttonotethereactionstereochemistry.Thecisdienophilereactstogivetwoproducts,bothofwhichhavetheesterfunctionscistoone
another,i.e.,thestereochemistrypresentintheoriginaldienophile(cis)iscompletelyretainedintheproducts.Inthesameway,thetransdienophile
isomergivesasingleproduct,whichhastheesterfunctionstranstooneanother.Inbothinstances,thestereochemicalrelationshipsoftheesterstoone
anotherinthereactantare100%retainedintheproduct.
Thissignifiesthattheadditiontothedienophile(analkene)hasoccurredwithsynstereospecificity.Recallthatsynstereospecificreactionsaretypically
associatedwithconcertedmechanisms.Theobservedreactionstereochemistryisfullyconsistentwiththepostulatedconcertedmechanism.Similar
resultshavebeenobservedforawidevarietyofDielsAlderreactions,whicharevirtuallyalwayssynstereospecific.
Ifthereactionhadbeenstepwise,forminganintermediatediradicalorotherintermediate,itwouldbeexpectedthatbothdienophileisomerswouldhave
formedamixtureofallofthethreeproducts.
Inthereactionofdimethylmaleatewith1,3cyclopentadiene,thefirstisomerisstronglypredominant.Theesterfunctionsinthispredominantisomerare
describedashavingtheendoconfiguration,whichtheesterfunctionsintheminorisomeraredescribedashavingtheexoconfiguration.Thesetwo
isomersaremorespecificallydiastereoisomers.
Typically,DielsAlderreactionshaveapreferenceforplacingsubstituentsintheendoconfiguration.[Wewillnotpursuethesubjectofwhythisis,at
present]
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