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1. ElectrophilicAddition.Animportantfeatureofalkene
reactivityisanabilitytoreactwithavarietyofelectrophilic
reagents,thosereagentsattractedtothesourceofextraelectron
density.Inanalkene,the2pz2pzbond(arelativelyweak
covalentbondduetothepoorsidetosideoverlapoftheporbitals),
servesassuchasource.Itisconcentratedaboveandbelowthe
molecularplaneandisthereforeaccessibleforthereactions.
Formationofvarietyofacyclicandcyclicintermediatesispossible.
2.
Examplesofcyclicintermediates.(Notethatthefollowing
alkeneisassumedtohavereacted:
'R
a.Epoxides.Thisintermediateisformedinareactionofan
alkeneandaperoxyacid,RCO3H.Aprotonatedepoxideisan
intermediateinformationofdiols.
H
O
O+
H
R
H
R'
R
H
R'
b.Mercuriniumion.Thisionisformedinthereactionofan
alkeneandmercuricacetate.
Symmetricalmercuriniumion
+ (CH CO
3
2
Hg
R'
(CH 3CO 2 )
Hg
R
H
R
H
R'
Ifoneofthealkenecarbonsisbestabletosustainthepositive
charge,theintermediatewillbeasymmetrical,withonlyapartial
bondbetweenthatcarbonandmercuryion.Thecarbonbestableto
sustainthepositivechargewillbearpartialpositivecharge.
Inthenucleophilicopeningofthemercuriniumion,thiscarbon
willbethepreferredsiteofnucleophileattack.Thus,theopening
oftheionisregioselective.
c.Haloniumions.Theseareformedwhenanalkenedisplaces
ahalideanionfromahalogenmolecule.Thebromoniumionis
shown.Justlikemercuriniumions(see2babove),asymmetrical
haloniumionsexist.
Symmetricalbromoniumion
Br
Br
H
R
H
R'
R'
d.Oxomanganeseanion.Thisintermediateisformedin
reactionofanalkeneandapermanganateanion,MnO4.Justlike
anepoxide,thisintermediateishydrolyzedtoadiol.
O
O
Mn
O
H
O
H
R
R'
e.Oxoosmiumcomplex.Thisintermediateisformedin
reactionofanalkeneandaosmiumtetroxide,OsO4.Justlikean
epoxidesoroxomanganeseanions,thisintermediateishydrolyzedto
adiol.
O
O
Os
O
H
O
H
R
R'
3.
Examplesofacyclicintermediates.
a.Carbocations.Theseareformedinreactionofanalkene
andanacidicelectrophilicreagent.Maybepresentinelectrophilic
additionsofotherreagentswhenaparticularlystablecarbocationis
formed.
H
R
H
R'
b.Alkylhydrogensulfates.Theseareeasilyhydrolyzedin
neutralH2Otoyieldalcohols.Theyareesters,productsofa
reactionofalkenesandconcentratedsulfuricacid,whentheamount
ofwateravailableforhydrolysisoftheesterislow,andarethe
resultoftrappingoftheintermediatecarbocationwiththe
hydrosulfate,aconjugatebaseofthesulfuricacid.Theeaseof
hydrolysisofhydrogensulfateisentirelyduetothefactthatthe
hydrosulfateisaweakbaseandhenceagoodleavinggroup.
H
R
R'
O
H
S
O
c.Organomercuricsalts.Theseareformedinareactionofan
intermediatemercuriniumionwithanH2Onucleophile.Theyare,
afteralossofaproton,reducedbysodiumborohydride,NaBH4,to
yieldalcohols.
Hg(OAc)
R
H
H
R'
OH2+
d.Alkylboranes.Formedinareactionofanalkenewith
diborane,(BH3)2.SubsequentlyoxidizedbyH2O2/HOtoyield
alcohols.
BH2
R
H
R'
4. Generalmechanismofelectrophilicadditionofacidic
reagents.a.Scheme:
1.Slow,usuallyreversibleprotonationofthealkene.The
reversestep,elimination,iseffectivewhentheconjugatebaseofthe
acidisstrong.
H
R
H
'R
+B
R'
2.Fasttrappingofthecarbocationintermediatewithabase.
H
H
R'
R
H
H
R'
b.Definingcharacteristics:
i. Acidicreagentmustbeused.Alkenesareweakbases
andrequirestrongacidsfortheprotonationtobeeffective.
ii. Rearrangementsarecommon.Justlikeinsubstitutionand
eliminationreactions,therearrangementsreflectthepresenceofan
carbocationintermediate.
iii. Orientation.Markovnikovaddition,withtheproton
foundontheleastsubstitutedcarbon,isobserved.Again,themost
stablecarbocationisproducedinStep1,leadingtothepositive
chargebeingdevelopedonthemostsubstitutedcarbon.
5. Othersyntheticreactionsinvolvingtheelectrophilic
additiontoadoublebond.
a.Acidcatalyzedhydration.Alkenesareeasilyhydratedby
waterinthepresenceofastrongmineralacid,usuallysulfuric,to
givealcohols.Sincetheformationofthealcoholistheresultof
trappingofthecarbocationintermediatewiththewaternucleophile,
thereactionisreversibleandrearrangementsarepossible.Thus,
thisreactionisnotstereoselectiveorspecific.But,itis
regioselective,sincetheMarkovnikovproductisformed,with
incomingH+placedontheleastsubstitutedcarbongivingamost
stablecarbocationintermediate.
b.Oxymercurationdemercuration.Alkenesarecapableof
addingmercuricacetateyieldingcyclicmercuriniumion.Ifthe
reactioniscarriedoutinthepresenceofmoisture,waterwillserve
asanaddednucleophileandopenthemercuriniumiontogivea
protonatedhydroxymercuricsaltwhichis,afteralossofproton,
reducedwithNaBH4togiveanalcohol.
Hg(OAc)2
OAc
H
R
R
OH2+
H2O
H+
H
R
OH
R
OH2+
Hg(OAc)
Hg(OAc)
H
Hg(OAc)
Hg (OAc)
NaBH4
H
R
OH
Theopeningofthemercuriniumionproceedsinthe
Markovnikovfashion,withtheincomingH(thistimeasahydride)
beingplacedontheleastsubstitutedcarbon.Thereactionis
regioselectivesincethewaternucleophilewillattackthecarbonbest
abletosustainthepositivecharge(see2babove).Itisalso
diastereoselectiveandstereospecificsinceitrepresentsanoverall
antiadditiontothedoublebond.
c.Hydroborationoxidation.Alkenesarecapableofadding
diboranetoyieldalkylboranes.Diboraneisthedimerofa
hypotheticalborane,BH3,astructurefeaturinganunusual2
electron,3centerbond,wherehydrogenexistsasahydrideto
satisfytheoctetrequirementofboron.Intermediatealkylboraneis
notisolatedbutisoxidizedinsituwithalkalineH2O2toyieldan
alcohol.Asin5b,thiscorrespondstoformalhydrationofthe
alkene.Mechanism:
H
R
B H
B2 H6
THF
R
NotethattheTSfeaturesacarbonwithpartialcarbocation
character.Thus,BH2fragmentwillbedirectedontotheleast
substitutedcarbonandthehydrideontothemostsubstitutedcarbon
(inordertostabilizetheincipientcarbocation).Inthefinalproduct
(alcohol)thehydroxygroupwillreplacetheBH2groupgivingrise
toanoverallantiMarkovnikovadditionofH2Otoanalkene.Thus,
thereactionisregioselective.Itisalsodiastereoselectiveand
stereospecificsinceitrepresentsanoverallsynadditiontothe
doublebond.
d.Additionofhalogens.Thisreactionisusedtoprepare
vicinaldihalides.
Br
'R
Br
Br2
H
R
R'
Br
H
R'
Br
OnlyBr2andCl2arereactivetowardsalkenesbythis
mechanism.Theevidencefortheformationofthehaloniumions
include:
i. Stereochemistry.Iftheacycliccarbocation
intermediateisformed,thereactionisexpectedtobenon
stereoselectiveorspecific,contrarytotheobservedresults.
ii. Formationofmixedadditionproducts.When
competingnucleophiles(intheformofnucleophilicsolventsor
addedsalts)arepresentduringhalogenaddition,mixedaddition
productsareobtained.Thisisknownastheeffectofadded
nucleophiles.See5ebelow.
Thereactionisregioselectivesincetheincomingnucleophile
willattackthecarbonbestabletosustainthepositivecharge(see2b
and2cabove).Itisalsodiastereoselectiveandstereospecificsince
itrepresentsanoverallantiadditiontothedoublebond.
Br
CH3
CH3
Br2
Br
CH3
BrBr
e.Formationofmixedadditionproducts.
+
Cl
Cl
Cl2
H 2O
H
H
H 2O
H
H
OH2+
Cl
H +
H
H
OH
Chlorohydrin
InthiscasetheadditionmodeisalsoMarkovnikovanditis
diastereoselectiveandstereospecific,withthehalogenofthe
haloniumionmovedtotheleastsubstitutedcarbon.Avarietyof
nucleophilessuchaswater,alcohols,halideorcyanideanionsmay
beused.
6.Oxidation.
a.Epoxidationhydroxylation.Alkenesreactwithperoxyacids
togiveanothercyclicintermediatesepoxides.Theseare
hydrolyzedunderacidicconditionsviaprotonatedepoxidetogive
diols.
Step1.Formationoftheepoxide;mCPBA=metachloroperoxybenzoicacid
O
mCPBA
C
O
O+
R'
H+
R
H
Cl
Cl
R'
R
H
R'
OH
OH
O+
H
R
H
R'
H2O
R
H
R'
OH 2+
H+
R
H
Step2.Acidcatalyzedhydrationandringopeningoftheepoxide.
H
R'
OH
Notethatthereactionrepresentsaantiadditionpathwayand
isadiastereoselectiveandstereospecificroutetodiols.Itisalso
regioselectivesincetheincomingwaternucleophilewillattackthe
sideoftheepoxidebestabletosustainpositivecharge.
b.KMnO4hydroxylation.AlkenesreactwithcoldalkalineKMnO4
toformdihydroxycompoundsdiols.Thereactioninvolves
formationofthecyclicoxomanganeseintermediatethatis
subsequentlyhydrolyzedinalkalinemediumtogivethedesired
product.Notethatthereactionrepresentsasynadditionpathway
andisadiastereoselectiveandstereospecificroutetodiols.
O
R
Mn
MnO4
OH
O
R'
OH
OH
H
R'
R'
c.OsO4hydroxylation.AlkeneswillalsoreactwithOsO4to
formdiols.Thereactioninvolvesformationofthecyclicosmate
esterintermediatesubsequentlyhydrolyzedinalkalinemediumto
givethedesiredproduct.Notethatthereactionrepresentsasyn
additionpathwayandisadiastereoselectiveandstereospecific
routetodiols.
O
R
Os
OsO4
H
R'
OH
O
H
R
R'
OH
OH
H
R'
d.OxidationwithhotKMnO4.Thisreagentbreaksthe
doublebond,andthereactionproductsdependonthestructureof
thealkene.
H2 CH3 C
MnO4
HOT
MnO4
HOT
CH(CH 3 )2
O
H2 CH3 C
OH
+H2 O+CO2
O
HO
CH(CH 3 )2
O
Notethatthepurposeofthereagentistoreplacethedouble
bondwithtwooxygenatoms.Therefore,onemayexpecttoseetwo
typesofproducts:aldehydesandketones.HotKMnO4isaharsh
oxidizer.Astheresult,theoxidationiscarriedoutfurtherwith
aldehydesbeingoxidizedtocarboxylicacidsandformaldehyde
(CH2O)toCO2andwater.Ketonesareresistanttooxidationand
arethereforefoundasproductsundertheseconditions.Bothacyclic
andcyclicalkenesaresubjecttodegradativeozonolysis.
e.Degradativeozonolysis.Ozone,O3,addstodoublebonds
forminganumberofintermediatesthemostimportantofwhichis
ozonide.ThisspeciesisreducedinsitubyZninthepresenceof
watertogivealdehydesand/orketonesdependingonthedegreeof
substitutionofthedoublebond.Eachdoublebondyieldstwo
fragmentsifitissubstitutedasymmetrically.Bothacyclicand
cyclicalkenesaresubjecttodegradativeozonolysis.
O
H2 CH3 C
O3
CH3
H2 CH3 C
CH3 O
Zn
H2O
H2 CH3 C
H3 C
H
O3
CH(CH 3 )2
O
O
O
CH(CH 3 )2
Zn
H2O
O
H
CH(CH 3 )2
O