11/16/2016

ComparingtheSN1andSN2ReactionsMasterOrganicChemistry

ComparingtheSN1andSN2Reactions
byJA ME S
inA L CO HO L S , A L K Y L HA L I DE S , O RG A NI C CHE MI S TRY 1 , O RG A NI C RE A CTI O NS , S TE RE O CHE MI S TRY

Hey!Youcannowdownloadafree1pageSummarySheetof
SN1vsSN2reactionscontainingallthematerialonthisseries
ofblogpostshere:DownloadSN1vsSN2SummarySheetPDF

SincewevegonethroughthedifferentfactorsthatimpacttheSN1
andSN2reactions,itsworthwhiletoreviewandsummarizethe
differentfactorsbehindeachofthesetworeactions.Butfirsthave
youeverheardthestoryofthecatsandthecomfychair?

IllustrationbythetalentedCanadianpoliticalcartoonistGraeme
Mackay.ThanksGraeme!
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ComparingtheSN1andSN2ReactionsMasterOrganicChemistry

Cat#1findsCat#2onhiscomfychairandwantstosit.Hehastwo
options.
1.HecanwaitforCat#2toleave,andthensitinthecomfychair.
2.HecankicktheCat#2outofhiscomfychair.
Thinkaboutthatforasecond.Inthemeantime,letscomparethe
SN1andtheSN2.

TheMechanism
TheSN2reactionisconcerted.Thatis,theSN2occursinone
step,andboththenucleophileandsubstrateareinvolvedinthe
ratedeterminingstep.Thereforetherateisdependent

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ComparingtheSN1andSN2ReactionsMasterOrganicChemistry

onboththeconcentrationofsubstrateandthatofthe
nucleophile.
TheSN1reactionproceedsstepwise.Theleavinggroupfirst
leaves,whereuponacarbocationformsthatisattackedbythe
nucleophile.
TheBigBarrierthisisthemostimportantthingtounderstand
abouteachreaction.Whatstheonekeyfactorthatcanprevent
thisreactionfromoccurring?
IntheSN2reaction,thebigbarrierissterichindrance.Since
theSN2proceedsthroughabacksideattack,thereactionwill
onlyproceediftheemptyorbitalisaccessible.Themoregroups
thatarepresentaroundthevicinityoftheleavinggroup,the
slowerthereactionwillbe.Thatswhytherateofreaction
proceedsfromprimary(fastest)>secondary>>tertiary
(slowest)
IntheSN1reaction,thebigbarrieriscarbocationstability.
SincethefirststepoftheSN1reactionislossofaleaving
grouptogiveacarbocation,therateofthereactionwillbe
proportionaltothestabilityofthecarbocation.Carbocation
stabilityincreaseswithincreasingsubstitutionofthecarbon
(tertiary>secondary>>primary)aswellaswithresonance.
Thedependenceofrateuponthesubstrate
FortheSN2,sincesterichindranceincreasesaswegofrom
primarytosecondarytotertiary,therateofreactionproceeds
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ComparingtheSN1andSN2ReactionsMasterOrganicChemistry

fromprimary(fastest)>secondary>>tertiary(slowest).
FortheSN1,sincecarbocationstabilityincreasesaswegofrom
primarytosecondarytotertiary,therateofreactionfortheSN1
goesfromprimary(slowest)<<secondary<tertiary(fastest)
RememberthatSN1andSN2reactionsonlyoccurforalkylhalides
(andrelatedcompoundsliketosylatesandmesylates).Iftheleaving
groupisdirectlyattachedtoanalkeneoralkyne,SN1orSN2will
notoccur!
TheNucleophile
TheSN2tendstoproceedwithstrongnucleophilesbythis,
generallymeansnegativelychargednucleophilessuchas
CH3O(),CN(),RS(),N3(),HO(),andothers.
TheSN1tendstoproceedwithweaknucleophiles
generallyneutralcompoundssuchassolventslikeCH3OH,
H2O,CH3CH2OH,andsoon.
TheSolvent
TheSN2reactionisfavoredbypolaraproticsolventsthese
aresolventssuchasacetone,DMSO,acetonitrile,orDMFthat
arepolarenoughtodissolvethesubstrateandnucleophilebut
donotparticipateinhydrogenbondingwiththenucleophile.
TheSN1reactiontendstoproceedinpolarproticsolventssuch
aswater,alcohols,andcarboxylicacids.Thesealsotendtobe
thenucleophilesforthesereactionsaswell.
Stereochemistry
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SincetheSN2proceedsthroughabacksideattack,ifa
stereocenterispresenttheSN2reactionwillgiveinversionof
stereochemistry.
Bycontrast,iftheSN1leadstotheformationofastereocenter,
therewillbeamixtureofretentionandinversionsincethe
nucleophilecanattackfromeitherfaceoftheflatcarbocation.
Sodoesthestoryaboutthecatsandthecomfychairmakesense
now?
IntheSN2,thenucleophile(Cat#1)formsabondtothe
substrate(comfychair)atthesametimetheleavinggroup(Cat
#2)leaves.
IntheSN1,theleavinggroup(Cat#2)leavesthesubstrate
(comfychair),andthenthenucleophile(Cat#1)formsabond.

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