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Unit 17: Carbohydrates

CHO
Introduction H OH

• Abundant in nature
HO H

C6H12O6 H OH
• Polyhydroxy aldehydes ketones
H OH

• Multifunctional CH2OH
Glucose
• Empirical formula CH2O
(dextrose or pentahydroxyhexanal)
• Product of photosynthesis
+ mH2O Cn(H2O)m + nO2
nCO2
• Source of energy

Cn(H2O)m + nO2 nCO2 + mH2O + energy


Unit 17: Carbohydrates

Classification
i) Monosaccarides ii) Complex carbohydrates

• Simple sugars • 2 or more simple sugars


• Cannot be hydrolysed to smaller • Can be hydrolzed to smaller
units units of simple sugars
• Eg. glucose, fructose • Eg. Sucrose (table sugar)
• Aldoses (aldehyde) ¾ disaccharide –2
• Ketoses (ketone) ¾ oligosaccharide – 3-8
• Number of carbons indicated by ¾ polysaccharide –>8
prefixes tri-, tetra-, pent-, hex- etc.
Unit 17: Carbohydrates

CHO
CH2OH
CHO
H OH
C O
H OH
HO H
HO H
H OH
H OH
H OH
H OH
H OH
H OH
CH2OH
CH2OH
CH2OH
aldopentose
aldohexose ketohexose
Unit 17: Carbohydrates

Monosaccharides

• Fischer projections used for depicting structures


• Each chirality center represented by a pair of crossed lines

press flat
Z
Z
W x
W X W X

Y
Y z Y

CHO CHO
CHO
H CH2OH H CH2OH
H
CH2OH OH
HO OH
Unit 17: Carbohydrates

• Fischer projections may be rotated by 180o, not 90o or 270o


• Holding one group steady, the other 3 groups can be rotated
clockwise or counterclockwise

180o 90o
CHO H
CHO OH

= H CH2OH
= OH CHO
H CH2OH CH2OH H

OH CH2OH
OH CHO

hold steady

CHO CHO

H OH = HO CH2OH

CH2OH H
Unit 17: Carbohydrates

Assigning R,S configuration:


i) Assign priorities to the substituents
ii) Perform one of two allowed motions to place the lowest priority
group at the top of the Fischer projection
iii) Determine the direction of rotation of the arrow that travels from
group 1 to group 2 to group 3 (R or S direction)

2 4
H
COOH
2 S 1
1
NH2 H
4 = HOOC NH2

CH3
CH3 Hold steady 3
3
Unit 17: Carbohydrates

• Carbohydrates with more than 1 chirality center are shown by


stacking the centers on top of each other
• Carbonyl carbon placed at or near the top

CHO CHO H

H OH H OH CH2OH
H
OH
HO H HO H = H CHO
=
OH
H OH H OH OH

H OH
H OH H OH
CH2OH
CH2OH
Truer conformation
Unit 17: Carbohydrates

D & L sugars:
• Simplest sugar (aldose) - glyceraldehyde (C3H6O3) occurs naturally
• Glyceraldehyde rotates plane polarized light in a clockwise direction
• (+)- glyceraldehyde, shown to be R-(+)- glyceraldehyde
• (L)-glyceraldehyde is therefore S-(-)-glyceraldehyde
• Most naturally occuring sugars are D sugars
• D- and L-glyceraldehyde are enantiomers
D-sugars: the –OH on chiral center furthest from C=O points to
the right
L-sugars: the –OH on chiral center furthest from C=O points to
the left

D&L assignment refers to the configuration furthest from the C=O.


It is not related to the direction of rotation of plane polarized light.
Unit 17: Carbohydrates

CHO CHO CHO


CHO

HO H H OH HO H
H OH

CH2OH CH2OH HO H H OH

D-glyceraldehyde L-glyceraldehyde H OH HO H

H OH HO H
CHO CHO

CH2OH CH2OH
H OH H OH
D-glucose L-glucose
H OH H OH

H OH HO H

CH2OH CH2OH

D-ribose L-ribose
Unit 17: Carbohydrates

CHO

Aldoses H OH D-glyceraldehyde
(L enantiomers not shown)
CH2OH

CHO CHO

R/L H OH HO H
2 D,L pairs of aldotetroses D-erythrose D-threose
2R H OH H OH

CH2OH CH2OH

4 D,L pairs of aldopentoses CHO CHO CHO CHO

• At C-4: all OH’s to the right R/L H OH HO H H OH HO H

• At C-3: 2R/2L
2R/2L H OH H OH HO H HO H
• At C-2: R/L
4R H OH H OH H OH H OH
“Ribs are extra lean”
CH2OH CH2OH CH2OH CH2OH

D-ribose D-arabinose D-xylose D-lyxose


Unit 17: Carbohydrates

CHO CHO CHO CHO

H OH HO H H OH HO H

8 D,L pair of aldohexoses H OH H OH HO H HO H

H OH H OH H OH H OH

• At C-5: all OH’s to the right H OH H OH H OH H OH

• At C-4: 4R/4L CH2OH CH2OH CH2OH CH2OH

• At C-3: 2R/2L D-allose D-altrose D-glucose D-mannose

• At C-2: R/L CHO


CHO CHO CHO

“All altruist gladly make H OH HO H H OH HO H

gum in gallon tanks” H OH H OH HO H HO H

HO H HO H HO H HO H

H OH H OH H OH
H OH

CH2OH CH2OH CH2OH


CH2OH

D-gulose D-idose D-galactose D-talose


Unit 17: Carbohydrates

Cyclic structures – Hemiacetal formation


• in aqueous solution, the open-chain monosaccharides are in equilibrium
with their internal hemiacetals
OH
O
H+ catalyst
+ R'OH
C H H O
OR' C
R H R

aldehyde hemiacetal H OH

HO H

• intramolecular nucleophilic addition of the C=O (C-1) to the: H OH

i) -OH on C-5 to form a α or β pyranose H OH


ii) -OH on C-4 to form a α or β furanose
CH2OH

α or β glucofuranose open-chained α or β glucopyranose


gucose
Unit 17: Carbohydrates

Glucose exists in aq. solution primarily in the pyranose form:

H O
C CH2OH
• Cyclization generated a new chiral
center at C-1, resulting in the formation of
H OH OH H

HO H = C a pair of diastereoisomers called anomers:


OH O
H OH
OH
• C-1 is the anomeric carbon
H OH
OH

CH2OH
CH2OH CH2OH

O H O OH

C and C
OH OH

OH OH OH H

OH OH

α-D-glucopyranose β-D-glucopyranose
Unit 17: Carbohydrates
OH

O
CH2OH CH2OH
OH

C O OH
HOCH2 CH2OH HO 72%
OH
HO H
= OH C
O
H OH
CH2OH OH
O
H OH OH HO

CH2OH CH2OH
OH

D-fructose 28%
Unit 17: Carbohydrates

H trans H cis

CH2OH H CH2OH H O
O
HO HO
HO H HO OH
H H OH
OH

H OH H H

α-D-glucopyranose β-D-glucopyranose
Melting point: 146oC Melting point: 148-155oC
Specific rotation [α]D: +112o Specific rotation [α]D: +18.7o

When a sample of either of the two pure anomers is dissolved in water, the optical
rotation slowly changes and ultimately reaches a constant value of +52.6o.
This phenomenon is known as mutarotation:
• Change in optical rotation due to slow conversion of the pure anomers into the
37:63 equilibrium mixture
• Occurs by a reversible acid or base catalyzed ring-opening of each anomer to the
open-chain aldehyde followed by reclosure
Unit 17: Carbohydrates

CHO
H
H
H OH
CH2OH H O CH2OH H O
HO HO H HO
HO H
HO OH
H OH H OH H OH
H OH
H OH H H

37.3%
CH2OH 62.6%
0.002%
All substituents on the ring
Are equatorial, thus least
sterically crowded and more
stable
(the most stable of the eight
D-aldohexoses)
Unit 17: Carbohydrates

Reactions of Monosaccharides
1. Glycoside formation
• Treatment of hemiacetal with an alcohol and acid catalyst yields an acetal
OH OR'

H+ catalyst
H + ROH H + H 2O
OR' OR'
R R

hemiacetal acetal

• Treatment of monosaccharide hemiacetal with alcohol and acid catalyst


yields an acetal in which the anomeric –OH is replaced by –OR
• The acetals are called glycosides
Unit 17: Carbohydrates

CH2OH O CH2OH
CH2OH O CH3OH, HCl O
HO + HO
HO
HO HO OCH3
HO OH
OH OH
OH OCH3

β-D-glucopyranose Methyl-α-D-glucopyranose Methyl-β-D-glucopyranose


33% 66%
• Glycosides are stable in water
• Glycosides are not in equilibrium with an open chain, i.e do not show mutarotation
• Aqueous acid reconverts the acetal to a monosaccharide (hydrolysis)
• Glycosides occur in nature, biologically important (eg. digitoxin)
Unit 17: Carbohydrates

2. Ester and ether formation


• Esterification occurs by treatment with an acid anhydride or acid chloride in
the presence of base
CH2OH CH2OCOCH3 O
O (CH3CO)2O
HO CH3OCO
HO OH pyridine, 0oC CH3OCO OCOCH3
OH OCOCH3

• Ethers are formed by treatment with methyl iodide and Ag2O (a base) –
Williamson synthesis
CH2OH CH2OCH3 O
O
HO Ag2O CH3O
HO CH3O
CH3I
OH OCH3
OH OCH3
Unit 17: Carbohydrates

3. Reduction
• Treatment with NaBH4 yields a polyalcohol called an alditol
• Occurs by reaction of the open-chain form in the aldehyde/ketone –
hemiacetal equilibrium
H O
C CH2OH

H OH H OH
CH2OH O 1. NaBH4
HO HO H HO H
HO 2. H2O
OH H OH H OH
OH
H OH H OH

CH2OH CH2OH

D-glucitol
(D-sorbitol)
Unit 17: Carbohydrates

4. Oxidation
• Several mild reagents can oxidize the aldehyde C=O to –COOH to yield
aldonic acids
• Test for reducing sugars – treatment with:
i) Tollens reagent - formation of silver mirror
ii) Fehling’s reagent and Benedict’s reagent - formation of red Cu2O
precipitate
• All aldoses are reducing sugars because they contain an aldehyde C=O
Unit 17: Carbohydrates

• Some ketoses (eg. fructose) are also reducing sugars


• Fructose readily isomerizes in basic solution by a series of keto-enol
tautomerism shifts to form the aldose which thus can reaact with Tollen’s,
Fehling’s or Benedict’s reagent
OH O
H
CH2OH C
C OH
H C H C OH
C O

HO H
HO H NaOH, H2O
HO H NaOH, H2O

H OH keto-enol H OH keto-enol H OH

tautomerism tautomerism
H OH
H OH H OH

CH2OH
CH2OH CH2OH

an enediol an aldohexose
D-fructose

Note: Glycosides are non-reducing because the acetal group is not hydrolyzed to an
aldehyde under basic conditions.
Unit 17: Carbohydrates

• Better yields of aldonic acids may be obtained by treatment with aqueous Br2
• Reaction is specific for aldose, ketose are not oxidized

O O
H HO
C C

OH OH H OH H OH

O HO H Br2, H2O HO H

OH
pH=6
HO HO H HO H
OH
H OH H OH

β-D-galactose
CH2OH CH2OH

D-galactonic acid
Unit 17: Carbohydrates

• treatment with warm dilute HNO3, aldoses are oxidized to dicarboxylic acids
called aldaric acids

O O
H HO
C C

OH OH H OH H OH

HNO3
O HO H HO H
Heat
HO OH HO H HO H
OH
H OH H OH
β-D-galactose
CH2OH C
HO O

D-galactaric acid
Unit 17: Carbohydrates

Periodate oxidation
• Oxidative cleavage of polyhydroxy compounds
• Uses aqueous periodic acid (HIO4)
• Breaks C-C bonds and produces carbonyl compounds (CHO, C=O & COOH)
• For every C-C bond broken, a new C-O bond is formed at each carbon
• Stoichiometry of reaction:

O
C OH
2 + HIO3 + H2O
+ HIO4 C
C OH
Unit 17: Carbohydrates

When 3 or more –CHOH are contiguous, the internal ones are obtained as formic acid

C
formaldehyde
H H
H +
O
H C OH
C Formic acid
+ 2HIO4 OH
H C OH H
+
H C OH O

formaldehyde
H C
H H
Unit 17: Carbohydrates

When a –OH is adjacent to the carbonyl of an aldehyde or ketone


(but not that of an ester or acid)
O

C
Formic acid
H OH
+
O
H O
C
C Formic acid
+ 2HIO4 OH
H C OH H
+
H C OH O

formaldehyde
H C
H H
Unit 17: Carbohydrates

C formaldehyde
H H
H +

H C OH O C O Carbon dioxide

+ 2HIO4
C O
+
H C OH O
formaldehyde
H C
H H
Unit 17: Carbohydrates

Periodic acid does not cleave compounds in which:

• the –OH groups are e separated by an intervening –CH2-group


• the –OH is adjacent to an ether or acetal function

H C OH

+ HIO4 no cleavage
CH2

H C OH
CH2OCH3

H + HIO4 no cleavage
CHOH

CH2R
Unit 17: Carbohydrates

Disaccharides Contain a β- or α- glycosidic acetal bond


between the anomeric carbon of one sugar and
an –OH group at any position on the other sugar
1. Cellobiose and maltose
• Contain a 1,4’-glycosidic acetal bond between 2 glucose units
• They are reducing sugars because the right-hand glucopyranose units have
hemiacetal groups, thus they exhibit mutarotation
• Celllobiose obtained by partial hydrolysis of cellulose, non digestible
• Maltose obtained by enzyme-catalyzed hydrolysis of starch, digestible
OH
OH

OH
O
O
HO
HO 4' 1
O HO H OH
HO 1 O
OH
OH 4'
HO OH O
H O
OH
H HO H
OH

OH
Cellobiose (1,4’-β-glycoside) Maltose (1,4’-α-glycoside)
[4-O-(β-D-glucopyranosyl)-β-D-glucopyranose] [4-O-(α-D-glucopyranosyl)-α-D-glucopyranose]
Unit 17: Carbohydrates

2. Lactose
• a 1,4’-β-linked glycoside, consisting of a unit of D-galactose and D-glucose
• A reducing sugar, thus they exhibit mutarotation
• Occurs naturally in human and cow’s milk

OH OH
OH
β-glucopyranoside
O

O
HO O
OH
HO OH
β-galactopyranoside H OH

Lactose (a 1,4’-β-glycoside)
[4-O-(β-D-glucopyranosyl)-β-D-glucopyranose]
Unit 17: Carbohydrates

3. Sucrose
• ordinary table sugar (from sugar canes or sugar beets), honey
• also called invert sugar because the sign of optical rotation inverts during
hydrolysis:
sucrose ([α]D= +66.5o) glucose/fructose mixture ([α]D= -22.0o)
• yields 1 equivalent fructose and 1 equivalent glucose upon hydrolysis
• 1,2’-glycosidic link between C-1 of glucose and C-2 of fructose
• Not a reducing sugar, do not exhibit mutarotation

OH

O fructose
HO Sucrose (a 1,2’-glycoside)
CH2OH
HO O
OH
1 2'
OH [2-O-(α-D-glucopyranosyl)-β-D-fructofuranpside

Glucose O CH2OH
OH
Unit 17: Carbohydrates

POLYSACCHARIDES

Cellulose: a 1-4’-O-(β-D-glucopyranodie) polymer


OH
OH
O OH
O
O OH
O
O
OH O
O
OH OH O
OH OH O

OH OH

OH

• Cellulose molecules also interact futher through hydrogen bonding

• Used primarily as structural material

• Imparts strength and rigidity