SESSION - 2023-2024

Topic - CONFIGURATION AND CONFORMATION OF

MONOSACHHARIDES

Under the guidence of Prof. Dr. Rjesh Ram SIr

Represented by - KAJOL
Class - B.Sc. III rd year
Semester- Vth
 TOPICS TO BE COVERED

1. IInttroduction

2. Types of Carbohydrate

3. IIntroduction of Monosachharides

4. Configurattiion of Monosachharide

5. Conformation of Monosachharide
• Introduction
• Carbohydrates like sugar, glucose, starch, cellulose, etc., provide us three basic needs of life,
namely,food(in the form of starch containing grains), clothing (cotton, linen and rayon are literally
cellulose) and shelter (wood used to make our houses and furniture is almost cellulose). Ribose and
deoxyribose are components of hereditary material nucleic acid (RNA and DNA). They are also
important to the economy of many nations. Table sugar, for example, is one of the most important
commercial commodities. In addition some commodities of daily use are paper, photographic
films,place lacquers, etc., derived from carbohydrate materials, as semisynthetic plastics.
• These were originally defined as compounds of carbon, hydrogen and oxygen with later two elements
the ratio 2:1 (water composition), having empirical formula Cn(H2O)m, hence named as hydrates of
carbon (in French, hydrate decarbon, meaning hydrates of carbon). For example, glucose and
fructose, C6H12O6,= C6 (H2O)6; sucrose C12H22O11= C12 (H2O)11, etc. However, the word
carbohydrate is a misnomer, as some members do not obey above definition (e.g., Rhamnose,
C6H12O5, rhamnoheptose C7H14O6, etc.) whereas some other compounds like formaldehyde
(CH2O), lactic acid, C3H6O3 [C3(H₂ O)3], are not carbohydrates but obey empirical formula Cn
(H2O)m.
• Structurally, carbohydrates contain only two main functional groups, viz., carbonyl and hydroxyl The
carbonyl group, however, does not occur in free form but forms intramolecular hemiacetal or acetal
linkages with -OH group (s). Further, they contain more than one asymmetric carbon atoms.
Accordingly, carbohydrates are defined as polyhydroxy aldehydes or Ketones or compounds which
give these on hydrolysis and contain atleast one asymmetric carbon atom. The name of carbohydrate
is still retained because of its simplicity and historical background. They are often called saccharides
(Latin,sachharum meaning sugar) because of the sweet taste of simpler members.
2. Classification of Carbohydrate
Carbohydrates are broadly divided into three main classes. These are:
1.Monosachharides. These are simplest carbohydrates known as simple sugars becase they `can not be
further hydrolysed into simpler sugars . They may be aldose or ketoses depending upon whether they contain
an aldehyde or a keto group (free or potential ).They can further subdivided into triose,tetrose, pentose ,and
hexose ,depending upon the nunmer of carbon atoms present in a particular monosachharidse;
a. Aldoses :- Those monosachharides having -CHO as a functional group are said to be aldose sugars .
Some aldose sugars are as given below,
Glyceraldehyde ,Erythrose , Threose , Ribose,Xylose,Arabinose, Glucose ,Mannose,Galactose etc. .
b. Ketoses :- Those monosachharides having ketone as a functional group are said to be ketoses. For
example , Dihydroxy acetone, Erythrulose,Ribolose,Xylulose,Fructose ,Sorbose etc. .
2. Oligosachharides : They are hydrolysed into a few monosachharides . They may be di-,tri-,and tetra
saccharide depending upon the number of monosachharide uits given by them on hydrolysis .For example,
Disachharide -Sucrose ,maltose ,lactose
Trisachharide - Raffinose (C18H32O16)
Tetrasachharide -Stachyose (C24H42O21)
3. Polysachharide These are the carbohydrates which can be hydrolysed to many (hundreds or even
thousands ) of monosachharide units . They are classified as homopolysachharide or
heteropolysachharide.depending upon whether they give only one or more than one kind of monosachharides
units on hydrolysis. Starch and cellulose are homopolysachharide ,and Inuline is the example of
heteroolysachharide .
3. Monosachharides
Monosachharides contain carbon atoms. Pentose and hexoses containig five and six carbon atoms
respectively are the most important .Monoachharidess are colourless ,crystalline compounds soluble in water but
insoluble in most of the organic solvents . Unlike disachharides , they crystallise with difficulty . When heated, they
char and give characteristic smell of burnt sugars .Chemically, monosachharides exhibit the reactions of both
alcohols and aldehydes/ ketones. Glucose and fructose are the representatives of aldoses and ketoses
respectively . It will be seen that the presence of -OH groups and =C=O group in the same molecule influence the
characteristics of two individual functional groups in a marked manner ,as evident from their chemical properties.
Glucose(C6H12O6), the most important and abundant monosachharide o
.In the combined form, it is present in many
glycosides,disachharides, and polysachharides .
The common sources of starch are maize, rice and potatoes.On complete hydrolysis, product is neutralised with
chalk and the mixture filtered. The filtrate is decolorised with animal charcoal and concentrated in vaccum pans.
Glucose crystallizes out and can be purified from the crude product by recrystallization from alcohol.
Physical Properties.
It forms colourless crystals, m.p. 146°C. It also forms monohydrate, m.p. 118°C. It is readily soluble in water,
sparingly soluble in alcohol but insoluble in ether. It is optically active and its solutions are dextro-rotatory, [a]D of a
fresh solution being + 112° (hence the name 'dextrose' for glucose). It is about three-fourth as sweet as cane-sugar
(sucrose).
Glucose finds a number of uses. For example, it is
(1) a food for children and invalids,
(2) A reducing agent in silvering of mirrors,
(3) Used in the manufacture of confectionery, in syrups, candies, jams, wine, beer, used in pharmacy, etc.
 Configuration of monosachharides
The simplest monosachharide is Glyceraldehyde .It contains one chiral carbon atom and hence exsists
in two enantiomeric forms , the (+)and the (-)glyceraldehyde. Their three-dimentional and Fischer
projection formulae are given below :

But the question now is which one of projection formula(I or II) represents (+)glyceraldehyde and which one
represents(-)glyceraldehyde . Since in the early days of development of stereochemistry,no mode was
available to determine the absolute configuration of the compounds , therefore, tto assign relative
configurations to various optically active compounds .
 .The (+)-enantiomer was given symbol D and was assigned
configuration in which the OH group lies towards right and Hatom lies towards left ,the CHO lies at the top and
CH2OH lies at the bottom of the Fischer projection .On the other hand ,(-)-glyceraldehyde was given symbol L
and was assigned the configuration (II) in which the oh lies towardsleft and H lies towards right .
Any compound that can be prepared from,or converted into D(+)-glyceraldehyde will belong to D-series and
similarly any compound that can be prepared or converted into(-)-glyceraldehyde will belong to L-series .
However, in 1951, Xray diffraction studies by Bijvoet proved that the arbitrarily assigned configurations of (+) and
(-)-glyceraldehyde actually represent their correct absolute configurations. If the configuration of glyceraldehyde
is correct, then the derived relative configuration of all other compounds must also represent their correct
absolute configurations. Thus ,the chiral carbon atom of D-glyceraldehyde and L-glyceraldehyde serve as
configurational reference points for all monosachharide.
Thus, a monosachharideis given
D-configuration, if the -OH group at the penultimate carbon like that in D(+)-glyceraldehyde lies on the right hand
side. On the other hand, it is assigned L-configuration if the -OH group on the penultimate carbon like that in L(-)-
glyceraldehyde lies on the left hand side
Further, it may be noted that the symbols D and L just refer to the configuration of the compound and as such
has no relationship with the sign and magnitude of optical rotation ,(+) or (-).
 Configuration of D-Aldoses

The configuration of D-aldoses such as tetroses , pentoses and hexoses can be easily derived from D(+)-

glyceraldehyde by using the following guidelines: Whenever a lower aldoses is converted into a higher

aldose, a new chiral centre is introduced next to the -CHO group. Therefore ,two new stereoisomeric higher

aldoses are formed which differ in configuration only at C2 but have the same configuration at the rest of

the chiral carbon atoms from which it is derivedas shown below .

 Configuration of D-ketoses
By following the same guidelines , the configuration of D-ketopentoses and D-ketohexoses can be easily
derived as shown below :
 Conformation of monosachharides

The relative position taken by singly bonded atoms by rotation around a carbon -carbon single bond is called
conformation and the process is known as conformational isomerism or conformational analysis . The infinte
nuber of arrangement of the atoms in space due to rotation about σ-bind are called conformation or rotational
isomers . Conformational isomers can be interconverted by simple rotation around sigma bonds

.
Pyranose and Furanose forms can exist in different conformers and one can interconvert between the different
conformations if an energy requirement is met for the furanose system there are twopossible conformers ;
Twist (T)and envelop (E) . In the pyranose system five conformations are possible ; chair(C), boat (B), stew (S),
half chair (H) or envelop(E ) .

In all case there are four or more atoms that make up a plan . In order to define which atoms are above and

below the plane one must orient clockwise when looking from top , Atoms above the plane are prefixed as a

superscript and atoms below the plane are suffixed as a subscript . If the ring oxygen is above or below the

plane it must be prefixed or suffixed appropriately .

 CONFORMATION OF α-and β-D(+)- Glucopyranose
Glucose and other carbohydrates are the best representes in the terms of their conformations . Although both
chair and boat forms are theoritically possible , glucose exist in the chair forms as shown by X-ray analysis .
Since glucose is the most stable of all naturally occuring monosachharides , therefore the -OHgroups at
C2 ,C3 ,C4 and the CH2OH at C6 assumed to be the more stable equatorial orientation . Further since an
equilibrium mixture of D(+)- glucose contais about 64% of the β-form and 36% of the σ-form , therefore ,β-form is
more stable than the σ-form as such the -OH group at C1 in β-D(+)-glucopyranose should also be equatorial
while in the α-form , it must be axial .In the α-form ,C1-OH is axial .It ,therefore , suffers 1,3 -diaxial interaction
with axial hydrogens at C3 and C5 while no such interactions are present in the β-form. Consequently ,β-D(+)-
glucopyranose is thermodynamically more stable than α-D-glucopyranose .
In the light of above discussion ,the conformations of α-D(+)-glucopyranose and β-D(+)-glucopyranose are given
below :
 CONFORMATIONS OF α-AND β-D(-)-FRUCTOSE
Like glucose ,fructose also exists in the chair conformation . The chair conformations of α- and β-D-
fructopyranose are given below :
It may be pointed out here that when the bulky CH2OH alone or along with one or more OH groups are

present in the less stable axial orientation ,ring flipping occurs to avoid sever 1,3 -diaxial interactions . As a

result , the monosachharides prefer to exist in the reverse chair conformation called 1C rather than in the

normal chair conformation called C1 .In the light of the above discussion , the 1C conformations of α- and
β-fructopyranose are given above .