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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
Classification
i) Monosaccarides ii) Complex 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
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
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
2 4
H
COOH
2 S 1
1
NH2 H
4 = HOOC NH2
CH3
CH3 Hold steady 3
3
Unit 17: Carbohydrates
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
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
• 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
H OH HO H H OH HO H
H OH H OH H OH H OH
HO H HO H HO H HO H
H OH H OH H OH
H OH
aldehyde hemiacetal H OH
HO H
H O
C CH2OH
• Cyclization generated a new chiral
center at C-1, resulting in the formation of
H OH OH H
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
CH2OH O CH2OH
CH2OH O CH3OH, HCl O
HO + HO
HO
HO HO OCH3
HO OH
OH OH
OH OCH3
• 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
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
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
H C OH
+ HIO4 no cleavage
CH2
H C OH
CH2OCH3
H + HIO4 no cleavage
CHOH
CH2R
Unit 17: Carbohydrates
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
OH OH
OH