AlkeneReactions.

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