Carbohydrates are molecules with the chemical formula Cn(H2O)n (n ≥ 3) or

derivatives of such molecules. Carbohydrates are the most important source

of energy in human nutrition but they play other roles as well: structure
(wood, chitin), recognition (cell surface carbohydrates), and protein folding.
The word sugar, used in biochemistry, has the same meaning as
carbohydrate. The word carbohydrate comes from the summary formula
Cn(H2O)n.
This class again has a very significant board component - don’t neglect it.

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The simplest sugars are called monosaccharides, which have a straight
(unbranched) chain of carbons that is not interrupted by oxygen atoms.
Monosaccharides are carbonyl (aldehyde or ketone) derivatives of straight-
chain polyhydroxy alcohols (polyols) that contain at least three carbon
atoms. That is, all carbons of a monosaccharide have a hydroxyl group
except the first or the second, which instead have a carbonyl group.
Glycerol is a three-carbon polyol since it has a hydroxyl group on each one of
its three carbons. It has two monosaccharides as derivatives.
Its aldehyde derivative is glyceraldehyde: it carries an aldehyde group
instead of one of the hydroxyls. Its ketone derivative is dihydroxyacetone: it
carries a ketone group instead of one of the hydroxyls. Thus,
monosaccharides can either be aldoses (the carbonyl group is an aldehyde
function) or ketoses (the carbonyl group is a keto group).

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Carbohydrates have very many stereoisomers. Each carbon (apart from the
ones at the ends) has two possible configurations).
The nomenclature of carbohydrates uses the DL nomenclature (the same
system as for amino acids). Glyceraldehyde, the smallest aldose, exists in
two forms (enantiomers) and is historically the basis for assigning the D-
and L- configuration.
An easy way to recognize D- and L- configuration is from the Fischer
projection: Sugars are drawn with the most highly oxidized group (the
carbonyl) as far towards the top as possible. Again, at each C atom,
horizontal bonds come towards you while vertical bonds go away from you.
If the alcohol group of the bottom most chiral carbon (= the chiral carbon
furthest from the carbonyl group) points to the right, then the sugar is called a
D- sugar (e.g. D-glyceraldehyde), if it points to the left, then the sugar is an L-
sugar.
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This chart shows all D-aldoses with up to 6 carbons (= trioses, tetroses,
pentoses and hexoses), together with their common names. The aldoses
with names framed in red are common in our metabolism and nutrition.
The other D-aldoses do exist in nature but they have very specialized roles.
L-aldoses (and generally, L sugars) are rarely found in nature (like D-amino
acids).

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This chart shows all D-ketoses with up to 6 carbons together with their
common names. The ketoses with names framed in red are common ketoses
in our metabolism and nutrition.
Sugars with up to nine carbons commonly occur in cells; larger ones are
rare.

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Sugars can do some very interesting chemistry.
Any alcohol can react with any aldehyde to form a hemiacetal. This reaction
is reversible (under physiological conditions).
This is the most important reaction that the aldose carbonyls undergo - it
leads to their cyclization (see the following).
(The ‘electron arrows’ on the left of the equation serve to understand the
mechanism of the reaction - we will talk about them later.)

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Aldoses - if they are five carbons or longer - often form a hemiacetal within
the same molecule. This makes the molecule circular. The circular form of
glucose is called glucopyranose (because of its structural similarity to pyran).
The circularization introduces one additional chiral center at the so-called
anomeric carbon. The configuration of this newly formed chiral center is
denoted either alpha or beta.

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The alpha and beta stereoisomers of a sugar are called anomers. The two
anomeric forms of a sugar are freely interconvertible in solution - usually,
they exist in an equilibrium. If the anomeric hydroxyl group is on the same
side of the ring as the C-6 hydroxymethyl group, then the configuration of the
anomeric carbon is called beta.

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Pyranoses (circular sugars with a six-membered ring) can have two different
types of conformations (shapes) in solution that are energetically
acceptable, the chair conformations and the boat conformation.s The chair
conformations are the more favourable ones. The conformations are freely
interconvertible and in equilibrium in solution.
There are two different chair conformations (see next slide) and three
different boat conformations for each pyranose.

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Pyranoses have two different chair conformations that are interconvertible.
The two chair conformations differ in the positions of substituents in axial and
equatorial positions. The substituents that are equatorial in one
conformation are axial in the other conformation. This is why the change of
one chair conformation into the other is called inversion. The more stable
conformation is the one with large substituents in equatorial positions. In this
case, the conformation with the hydroxyl groups in equatorial positions is the
more stable one (the upper image).
D-glucose is the only D-pyranose that can have all its substituents in an
equatorial conformation.

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Any alcohol can react with a ketone to form a hemiketal. This reaction is
reversible (under physiological conditions).
This is analogous to the formation of a hemiacetal. But, compared to a
hemiacetal, the hemiketal carbon is not bonded to any hydrogen atoms.

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Ketoses of an appropriate length (usually hexoses and heptoses) can form a
hemiketal within a ketose molecule. This reaction makes the molecule
circular. The circular form of fructose is called fructofuranose (because of its
structure similar to furan). The alpha and beta conformations of the anomeric
carbon are determined as for the pyranoses.
http://instruct.uwo.ca/chemistry/223b-98/car
bos/image439.gif

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