CARBOHYDRATE

Reactions of
Monosaccharides

Reactions of Monosaccharides
sugars are multifunctional compounds; most exist
as cyclic hemiacetals
in solution, sugars are in equilibrium with their openchain aldehyde or ketone forms
undergo most of the usual reactions of ketones,
aldehydes and alcohols
Side rxns: 2 common base-catalyzed side reactions:
;

Epimerization

Enediol Rearrangement

Epimerization
proton alpha to carbonyl group (in aldehyde or ketone)
is reversibly removed; form an enolate - C2 no longer
chiral.
reprotonation can occur on either side of the enolate to
give either configuration
products are mixture of original sugar and its C2 epimer

Epimerization

Enediol Rearrangement
moves the carbonyl group up and down the chain
conversion of aldose to ketose

Reduction of Monosaccharides
C=O of aldoses or ketoses can be reduced to C-OH
by NaBH4 or H2/Ni.
Name the sugar alcohol by adding -itol to the root
name of the sugar; commonly known as an alditol.
Reduction of D-glucose produces D-glucitol,
commonly called D-sorbitol.
Reduction of D-fructose produces a mixture of
D- glucitol and D-mannitol.

HC
H
CH2OH
HO
HO

O
OH
OH

H
HO
H
H

O
OH
H
OH
OH

CH2OH

H2, Ni

CH2OH
-D-glucopyranose

open-chain aldehyde

H
HO
H
H

OH
H
OH
OH
CH2OH

D-glucitol
(D-sorbitol)
an alditol

CH2OH
HOCH2

O
HO

HO
H
H

OH

H
OH

CH2OH

O
H
OH
OH

CH2OH

open-chain keton

-D-fructofuranose
NaBH4
CH2OH

mixture of alditol

H
HO
H
H

OH
H
OH
OH
CH2OH

D-glucitol

CH2OH

HO
HO
H
H

H
H
OH
OH
CH2OH

D-mannitol

Oxidation by Bromine

Oxidation by Nitric Acid

Oxidation by Tollens Reagent

Ag(NH3)2+ -OH (strong basic condition) --- give Ag (silver mirror)
promotes epimerization & enediol rearrangements
- therefore, cannot distinguish aldoses & ketoses
Sugars that reduce Tollens reagent are called Reducing

sugars

Formation of Glycosides: Sugar acetals

Aldoses & ketoses are converted to acetals by treatment
with alcohol in the presence of acid.
-glycosidic bond

H
CH2OH
HO
HO

CH3OH, H
OH

OH
H

H2O, H

CH2OH
HO
HO

OCH3
OH

hemiacetal

methyl -D-glucopyranoside
(acetal)
+
-glycosidic bond

H
CH2OH

methyl -D-glucopyranoside
(acetal)

HO
HO

O
H
OH

OCH3

Glycosides

Aglycone is the term used for the group bonded to the

anomeric carbon.

Glycosides

Nonreducing Sugars

Glycosides are acetals, stable in base, so

they do not react with Tollens reagent.
Disaccharides and polysaccharides are
also acetals, nonreducing sugars.

Ether Formation

Osazone Formation

Ester Formation

Ruff Degradation

Aldose chain is shortened by oxidizing the

aldehyde to -COOH, then decarboxylation.

Kiliani-Fischer Synthesis

This process lengthens the aldose chain.

A mixture of C2 epimers is formed.

two epimeric
cyanohydrins
* Pd/BaSO4 to avoid over reduction