CHEM210 [CHAPTER5:MASTERINGNOMENCLATURE

SkillsyoumustmasterforChapter5:

1. Beabletorecognizechiral/stereocenterswithinmolecules,bothsimpleandcomplex
2. Learnhowtoproperlyillustratestereogeniccenterswedgesandhashes
3. Beabletodrawthemirrorimageofamoleculeanddeterminewhetherthemoleculeischiralornot.Ifthe
moleculeisknowntobechiral,usethisskilltoillustratetheenantiomer.
4. AssignR,Sconfigurationstochiral/stereogeniccenters

LOCATINGCHIRALCENTERS

Bydefinitionastereogenic/chiralcarboncenterissp3hybridizedandhasbondstofourdifferentgroups.Given
thetaskoffindingallthestereogenic/chiralcenterswithinamoleculeyoucanquicklyignoreallsp(twogroups)
or sp2 (three groups) carbons as possibilities. Likewise all CH3 and CH2 groups can be ruled out as well.
Inspecttheremainingsp3carboncentersandensurethatfourdifferentgroupsareattached.

ConsiderthepotentanalgesicDarvon;locateallthechiralcentersinthismolecule.

Step1:Ruleoutallnonsp3carbonatoms. Step2:RuleoutallCH3andCH2groups.

Step3:Inspecttheremainingcarbonstoensuretheyhavefourdifferentbonds

Darvoncontainstwochiral/stereogeniccenters

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Problem1:Findallthechiral/stereogeniccentersinthefollowingmolecules

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ILLUSTRATINGMIRRORIMAGES

Themostcommonwayweuseinlecturetodrawmirrorimagesistoplaceamirrortotheimmediaterightof
thestructure.Keepinmindwecanplacethemirroranywheretomakethereflectioneasier.

Considerthestimulantamphetaminewhichexistsasapairofenantiomers.

Todrawtheenantiomerwecanplacethemirrorinseverallocations:

Mirror behind the molecule: Here the
majority of the molecule remains the
same;weonlyneedtoreversethewedge
toadashedbond.

Mirrortothesideofthemolecule:Inthis
casethemoleculeisswitchedlefttoright
andthewedgeremainsawedge.

Mirror beneath the molecule:Similarto

thepreviousexampleexceptthemolecule
is flipped up and down. The wedge
remainsawedge.

Aswaspointedoutinlectureallofthesemoleculesareenantiomersfortheamphetaminemoleculepictured
above:

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Formoleculeswithonechiral/stereogeniccentertherearesomeusefuloperationstolearnregardingillustrations:

Considerthefollowingenantiomerof2butanol.Rememberthatinskeletalstructuresthehydrogenisnot
shownonthechiral/stereogeniccenter:
OH HO H

Flipanyonepairofgroupsaboutthechiral/stereogeniccenteryouconvertthemoleculetoitsenantiomer:
flip
flip
HO H H OH HO H HO
and so on
(R) (S) (R) (S) H

enantiomers enantiomers


Flipanytwopairsofgroupsaboutthechiral/stereogeniccenteryousimplyreillustratethesamemolecule:
flip
flip
HO H H OH HO H
and so on
(R) (R) flip (R) HO (R) H

flip

identical identical



Problem2:Drawtheenantiomerofeachofthefollowingcompounds:

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ASSIGNINGCONFIGURATIONUSINGTHECAHNINGOLDPRELOGPRIORITYRULES

STEP1 STEP2 STEP3 STEP4 STEP5
Identifythefour Assignpriorityto Iftwoatomshavethe Rotateorredrawthe Determinewhether
atomsdirectly eachatombasedon sameatomicnumber, moleculesothat the123sequenceof
attachedtothechiral atomicnumber. movetothenext priority4ispointing prioritiesfollowsa
center. Highestatomic atomoutlookingfor backwards. clockwise(R)or
numberispriority1 thefirstpointof Becareful!Usea counterclockwise(S)
andthelowest difference. methodthatworks order.
atomicnumber Remembermultiple foryou!
(usuallyH)receives bondsaretreatedas
priority4. multiplesinglebonds.

Easyexample:Assigntheconfigurationtothechiralcenterinthisstereoisomerof2butanol:

Firstfindthechiralcenter!
Beforeapplyinganyofthesteps,rememberthatthefourth
bondtothechiralcarbonistoahydrogennotshownonthe
skeletalstructure.Drawinthishydrogenusingtheproper
wedge/dash/line.

Step1:Identifythefouratomsattachedtothechiralcenter.In
thiscasetheyareC,C,OandH


Step2:Assignprioritybasedonatomicnumber.Ohasthe
1 4
highestatomicnumberandgivenpriority1.LikewiseHhasthe
lowestatomicnumberandgivenpriority4.Wehaveatie
betweenthetwoCatoms.
Step3:MovingtothenextatomoutfromthetwoCatomsthat
aretiedweseetheleftcarbonhasonlyhydrogensattached
(lowestpriority)whiletherightChasanotherCattached.We
assignpriority2totherightCand3totheleftC.
Step4:Sowehavetheprioritiesaboutthechiralcenter.Inthis
1 4 easyexamplethe4priorityisalreadygoingtotheback.

3 2

Step5:From123wearegoingclockwiseandcanassignthis
chiralcentertheRconfiguration.

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Whatifthe4priorityisnotgoingbackwardasdrawn?Whatifthechiralcenterisdifficulttovisualizewithina
largecomplexmolecule?Therearetwomethodstochoosefrom.Usethemethodthatiseasiestforyouor
applythebestmethodtothesituation.

Method1:MostcommonproblemThe4priorityispointingforward.
Solution:Donotredrawthemolecule.Insteaddeterminewhether123isclockwiseorcounterclockwiseas
drawnandreversetheassignment.
Draw in missing H
OH - should be wedge OH
H

Assigning priorities:
1
3
OH
H 4
2 - remember C=C
becomes C
C
C
Going from 1-2-3 we are going clockwise

1
3
OH
H 4
2

Normally clockwise is R, but since priority 4 (H) is pointing

towards us we reverse the answer. The configuration of this
center is S.

Method2:Redrawthecenterasaseparatestructureusingonlytheprioritynumbers.Rememberflippingtwo
pairsofbondsreillustratesthesameconfiguration.Dothistogetthe4prioritypointingbackwardsortomake
theconfigurationeasiertovisualize.

Step1: Step2: Step3:

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Problem3:Assignconfigurationstothechiralcentersinthefollowingmolecules:

ChallengeProblem:Ifyougetthisoneyouhaveitmastered!Rememberthatyouhavea50:50chanceof
guessingrightevenifyouranalysisisincorrect,sodontrunoffandpartyyet.

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Lastskill:Drawingmoleculesofaparticularconfiguration.Thismaybethehardesttogiveyouadefinitivesetofrules
forsolving.Ifyoulookatthemoleculesyouvebeenassignedsofaryouseethatchiralityusuallyinvolvesafunctional
groupandmorespecificallyaheteroatom(nonCatom).Inmostofthesestructuresitiscustomarytousewedgesor
dashesfortheheteroatoms(usuallypriority1)orhydrogens(usuallypriority4)andleavethecarbonsintheplaneofthe
paperwhereverpossible.

Theeasiestwayfornovicestostartistosimplydrawoneenantiomerandassigntheconfiguration.Iftheconfiguration
doesnotmatchtheoneyouwereinstructedtodraw,simplyfliponepairofbondstoinvertthecenter.

Problem4:Drawmoleculesoftheindicatedconfigurationforthechiralcenter:

a. b.
asbothRandS(labeleach)
asbothRandS(labeleach)
c. d.

NaproxenDrawS
AsparticacidDrawS
e. f. CH3CHFBrDrawR

CarvoneDrawR

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KEY
Problem1:

Problem2:

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Problem3:

ChallengeProblem:

Problem4:

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