Organicchemistry Chapter6 Nucleophilic addition tothecarbonylgroup

Theangleofnucleophilicattackon aldehydesandketones
carbon buttheyalsoalwaysapproachfrom a
Nucleophilesnotonlyalwaysattackcarbonylgroupat
particularangle

atdoesnothaveparallelatomicorbitalsasthere is a nodehalfwaydownthebondsotheatomic
orbitalsarealready at anangleThenucleophilesattackalongtheaxisofthelargerorbitalintheHOMO

by hydride on aldehydesandketones
Nucleophilicattack

hydrideion H whichispresentinthesalt Nan hassucha highchargedensitythat itonlyreacts

asbase Itsfilled isorbitalis ofidealsizetoreactwithhydrogenatom'scontributiontothe s
orbitalof an H Xbond xcanbeanyatom butmuchtoosmalltointeracteasilywithcarbon'smore
diffuse zporbitalcontributiontotheLUMOCat oftheCeogroup

aBH4 l BE
H t H
borohydrideanion

I
 Theoxyanionproducedcanhelpwithstabilizingtheelectron deficientBHzmoleculebyadding
toitsemptyporbital Thenewtetravalentboroncantransferasecond Hatom withitspairof
ofaldehyde
electrons toanothermolecule

Examples ofreductionswithsodiumborohydride

Thewateroralcoholsolventprovides
theprotonneededtoformthe
fromthealkoxide
alcohol

sodiumborohydride isoneofthe weakerhydridedoners More powerfulone LiAlHq

canbeusedinwater reactviolently
withwater
Examplesofredution
Organicchemistry Chapter6 Nucleophilic addition tothecarbonylgroup
Addition
oforganometallicreagentstoaldehydesandketones
on
12TH met
T
I o01 it
ra it
time 7 J H
R H the
Ip
lithium and rn
agneiii
r narev.ciy
sitiie isand ice I orrt e bonds
in.net

in gainI air iomgin main viiiia r viii highlypolarizedtowardscarbon Theyareverypowerful

nucleophiles

separatesteps organometallicaredestroyedbywater

Li Me H ou
1
fastandexothermic
MeH lion
methane
watermustnotbepresentduringtheadditionofMeti
Theadditionofwaterorsometimesdilutedacid orammoniumchloride attheendofthereactionisknownas
workup i
organolithiums areusedusuallyatlowtemperature C782 inapnotiasolventsuchas Et
20andTHF
proticsolvents suchasHuo1alcoholshaveacidicprotons
alsoreactswithOzsohandledunder inertatmosphere Nuor Ar
dry of

organomagnesium reagentsknownasGrignard reagentsCR.mgx reactin asimilarway

Ph Br Mg phMgBr
ether
Organicchemistry Chapter6 Nucleophilic addition tothecarbonylgroup

Additionofwatertoaldehydesandketones

tHuo H H
µ r
f
expert13C
HT H
signal Bcsignalat
between Isozoo
ppm 83ppm
t Huo
on
pfkp K R
of
significantconcentrations hydrateare
generally
formedonlyfromaldehydes

no
a O_0 o H oH
Hidy II y two H O
a HowX
H
X
on
H H H H H H
attack
Formaldehyde is anextremelyreactivealdehydesas ithasno substituentstohinder

atstericeffect
stericandelectroniceffects
stericeffectsare concernedwiththesizeandshapeofgroupswithinmolecules
fromthewaythat electronegativity differencebetweenatomsaffecttheway
Electroniceffects result
electrons are distributed inmolecules Theycan bedividedintoinductiveeffects whichare consequence

ofthewaythatelectronegativity differencesleadto polarizationof 6 bonds andconjugation1

sometimes
calledmesomericeffect TattakixFKWhichaffectsthedistribution electrons in a bond
of
stericandelectroniceffectsare two ofthemainfactors dominatingthereactivityofnucleophilesand
electrophiles

ThelargerK themorethe
equilibrium is to theright

Thesamestructuralfeaturesthatfavour ordisfavourhydrateformationare
importantindeterminingthereactivityofcarbonylcompoundswithothernucleophiles
whethertheruinsarereversibleornot
Sterichinderanceandmorealkylsubstituentsmakecarbonylcompoundslessreactive
electronwithdrawinggroups andsmallringsmakesthemmorereactive
7morefavorableangleforthreememberedring