MONOSACCHARIDES

STEREOCHEMISTRY
Chirality
Enantiomers
Diastereomers
D- or L- configuration
Epimers
Anomers (α or β)
Stereochemistry

 Stereoisomer:
Isomeric molecule that have the same molecular
formula and sequence of bonded atoms, BUT
differ only in the 3D orientations of their atoms.

 Chiral:
Mirror image that is non-superimposable (E.g. a pair of
hands).
Chiral
 Stereochemistry
 Enantiomers:
 Pair of isomers that are (non-superimposable)
mirror images.

 Asymmetric (chiral) carbon:

 Carbon that bonds to four different groups.
 E.g. Glyceraldehyde which has a single
asymmetric carbon atom.
 Van’t Hoff rule:
The number of possible stereoisomers depends on
the number of asymmetric carbon atoms by the
formula 2n
(n = number of asymmetric carbon).
 Enantiomers

Enantiomers: stereoisomers that differ in

absolute configuration at ALL chiral centers.
 Chirality rules
 The most oxidized carbon is placed at the top and
designated as C-1.

 If there is more than one chiral C: The chiral carbon

furthest away from the most oxidized carbon
determines if it is D or L.

 D-configuration: OH-group on the right of the highest

numbered chiral carbon.

 L-configuration: OH-group on the left of the highest

numbered chiral carbon.
 C-1: the most oxidized carbon

4 chiral/assymetric carbon

D-Glucose: OH is on the
right of the
highest numbered
chiral carbon
Chirality rules

 In general, only the D-isomers are used

biologically, but there are many exceptions to this
generalization.

 Sugars can be conveniently written in two-

dimensional perspective known as Fischer
projections.
 Stereoisomers
 For the longer carbohydrates, there are more chiral
centers.

 What are the possible stereoisomers for longer

carbohydrates?
 The aldotetrose (4C) have 2 chiral carbons, C2
and C3 and there are 22 or 4 possible
stereoisomers.
 Aldopentoses (5C) with 3 chiral carbons will have
23 or 8 possible stereoisomers (four D forms and
four L forms).
 Stereoisomers
 Enantiomers:
Mirror-image stereoisomers (E.g. D-glyceraldehyde and
L-glyceraldehyde or D-erythrose and L-erythrose).

 Diastereomers:
Non-mirror image stereoisomers (E.g. L-erythrose and
D-threoses).
Enantiomers

Diastereomers
Stereoisomers that differ in absolute
configuration at at least one but NOT ALL
chiral centers.
Epimers

 A specific class of diastereomers that differ in

absolute configuration at only one chiral center.
 Example:
 glucose and mannose (C-2)
 glucose and galactose (C-4)
ALDOSES

D-Erythrose and D-Threose :

Diastreomers
Aldoses
 Figure shows the D-aldoses with three to six
carbon atoms.
 Note that from figure shown, only half the possible
isomers shown which is the D series. The L series
was not shown.
 The arrows indicate stereochemical relationships
(not biosynthetic pathways).
 The biologically most common aldoses are boxed.

D-Erythrose and D-Threose :

 Not superimposable on each other
 Not mirror image
 Diastereomers

D-Erythrose is the enantiomers of L-Erythrose.

D-Threose is the enantiomers of L-Threose.
KETOSES

The D-ketoses with three

to six carbon atoms.
The biologically most
common ketoses are
boxed.
 What happens if sugar
forms a cyclic molecule?
 Sugars especially those with five or six carbon atoms
normally exist as cyclic molecules.

 Cyclization takes place as a result of interaction between

functional groups with an alcoholic OH-group of another
carbon:
 C1 and C5 to form a cyclic hemiacetal (in
aldohexoses).
 C2 and C5 to form a cyclic hemiketal (in
ketohexoses).
 H H

C O + R' OH R' O C OH

R R
aldehyde alcohol hemiacetal

R R

C O + "R OH "R O C OH

R' R'
ketone alcohol hemiketal
 A sugar with six-membered ring
is known as pyranose in
analogy with pyran.

 A sugar with five-membered

rings are designated furanose
in analogy with furan.

 The cyclic form of glucose:

glucopyranose.

 The cyclic form of fructose:

fructofuranose.
Anomers
 Cyclization of carbohydrates to the hemiacetal creates
a new chiral center.

 The hemiacetal or hemiketal carbon of the cyclic form

of carbohydrates is the anomeric carbon.

 Carbohydrate isomers that differ only in the

stereochemistry of the anomeric carbon are called
anomers.

 The cyclic sugar can take either of two different forms,

designated as α or β.
 Anomers
β-D-Glucopyranose

anomeric
carbons

D-Glucose α-D-Glucopyranose
(linear form)
 Anomers α and β

The monosaccharides α-D-Glucopyranose and β-D-

Glucopyranose, drawn as Haworth projections and
ball-and-stick models, interconvert through the linear
form.