Review from Monday

Learning objectives

What is a carbohydrate and

how do we classify them
Fischerprojections Haworth
projections
Anomevil effett

I CHzOH
classify this monosaccharide Cs H2o

H I full name D ketopentose

H OH How
many chiral centers
5C 20H
2
How
many stereoisomers
2 n chiral centers Y
twist

it
iCHzOH
FISCHER PROJECTION
hemacetal

iii HAYFIECTION
anomeri carbon Both R S exist we call this anomers diasteromers

differing only the hemiantal carbon in monoscitharides

 α anomer has anomeri OH TRANI to CHzoltgro
p.pecis

iifi.EE iia.nniifiEij
α β
α D glucopyranose
end D 6 MEMBERED MONOSACIHARIDE RING
5 MEMBERED FURANOSE

Anomeric effect
α anomer
usually more stable
n hyperconjugation

ii.IEiffi iÉ nonconisation

69 OH 3
SNZ BACKSIDE ATTACK
On
recall
after
why is α not favored in D glucose

I
or
β α or
END RECAP
 wanna
ftp.iiiiiiiiiii.mn
EQUILIBRATION OF ANOMERI

Change in specific rotation

towards an equilibriumvalue

t.FI
5I
on

iii
α 53 when dissolved in H2o left standing

R
Glycoside alcohol acetal
sugar

sid nd
no T.fi

ftp.a
tonium

at
no.at
glucopyranoside
Ex What if R OH itself
HOW TO GENERATE
POLYSACCHARIDES

1 4

HYDROLYSIS

no men
CHIOH

i
galactose

EE a

Ekage no glucose

Ho OH

LACTOSE
EE s

PRACTICE
Show the Haworth projection of the B anomer chair
confirmation of D glucose
 IEiIiI
if iii
PROTECTING GROUPS SELECTIVITY IN CARBOHYDRATES

H
selectivity can be obtained
C hemiaretail CG
H
62 1 alcohol

Ethers esters acteal silan

Br benzylbromide

1 m sn aims
CH
CH

I
a
BULKY SUBSTITUENTS ARE REGIOSELECTIVE TOWARDS 1 CARBON

Bn Silanes

TBDPS CI
tert butyldiphenyl
silylchloride
c
si

one

Recall
I If

i i iiiiiii
 9H

iii
Oxidation of saccharides

Aidonia acids

JHNO

Aldaric acid
To

no
its
PRACTICE ON L SUGARI

Draw the 6memberedring form of L galantose in the lowest

prange energy chair conformation

IEEE
ff
it i ti i iitiiiii iii t
ation
gift's equforia OH
ff.it
H
ALDARIC ALDONIC ACIDS CAN CYCLIZE TO FORM 5 6 MEMBERED

CYCLIC ESTERS e.g LACTONES UNDER ACIDIC CONDITIONS

ii É
8lactom f lactone
α lactone
β lanton

i IEiiE itiEiii
FYI formed

Periodic Acid H Oy

RI Ryo
RI If
Rto
PT
Iff 03
iodic acid

Is F

H 0 2 H H

H
IF I H OH

Rules 1 chop bw contiguous CHOH Centers Ketism aldehyde

2 convert OH to c o ester ethers

3 Add new
oxygen to fill octet OH
if two vacancies add

H OH 2 A H
4104
8 O 1 0
CO2

H
 H

Hon H OH
4 2
4
IF I H H
H

Reduction of monosaccharides

CHzoH

REDUCING SUGAR
CHZOH
it
hemiacetal
Recall
Kiliani Fischer Synthesis
adds I carbon tosugar
RIA

if n
iti
ih an
i

a
N
H OH H OH H OH

OH
 Balott Babit
H N 0H It
Pii
OH

Ho H
TH Ha
H o H OH
H OH
OH OH
OH OH
Na Hg H2O
imidis acid Na Hg H2o
pH 5
PH3 5
RUFF DEGRADATION C

H DBraitted
ftp no it
H OH
130,1 H OH
OH I CHOH
OH