Cyclization of monosaccharides:

 In fact, such sugars tend to exist predominantly in cyclic form.

o What are the evidences that suggest that sugars exists in cyclic forms and not only as linear?
 Monosaccharides contain both a hydroxyl group, which can serve as a nucleophile, and a carbonyl group, which
is the electrophile.
 The hydroxyl group acts as the nucleophile during ring formation, so oxygen becomes a member of the ring
structure.
 They can undergo intramolecular reactions to form cyclic hemiacetals (from aldoses) and hemiketals (from
ketoses).
 Due to ring strain, the only cyclic molecules that are stable in solution are six-membered pyranose rings or
five-membered furanose rings. These names are derived from the parent compounds 'pyran' and 'furan‘.
o What about 3 or 4 or 7 membered ring structures? Can they be formed?Why are they not
common?
 The most common ring structure for aldohexoses is the pyranose ring structure that involves the first carbonyl
carbon and the hydroxyl group attached to the fifth carbon.
 The furanose ring structure is formed by interaction of carbonyl carbon with the hydroxyl group attached to the
fourth carbon.
 In glucose, carbonyl containing C-1 and the hydroxyl group on C-5 of D-glucose undergo intramolecular
hemiacetal formation
 Fructose exists in solution and in compounds as a furanose; however, in the crystalline state only the pyranose
ring is believed to exist.
 The furanose form is less stable than the pyranose strucure and is not very common among aldohexoses. Why?
 Regardless of whether hemiacetal or hemiketal is formed, the carbonyl carbon becomes chiral in this process,
and is referred to as the anomeric Carbon.
 A new asymmetric carbon is introduced in the molecule due to this rearrangement. As a result of this new
asymmetric centre, two isomers can be formed : α or β.
o How many asymmetric carbon does the cyclic form of aldohexose have? Now calculate the
possible number of optical isomers for the cyclic form of aldohexose.
 Isomeric forms of monosaccharides that differ only in their configuration about the hemiacetal or hemiketal
carbon atom are called anomers and the carbon is referred as anomeric carbon.
 Because these two molecules differ at the anomeric carbon, they are termed anomers of one another.
o Can anomers be called as epimers?
o Draw the Cyclic Fischer Projection and Haworth’s projection of D-Glucose and L-fructose.

 Conformational structure:
 The six-membered pyranose ring is not actually planar, but usually assume the stable chair conformation.
 The five-membered rings are very close to planar, but the pyranose rings adopt a chair-like conformation, and
the substituents assume axial or equatorial positions to minimize steric hindrance.
 The axial substituents project almost parallel with the vertical axis through the ring
 The equatorial substituents project roughly perpendicular to this axis.
 Substituents in the equatorial positions are less sterically hindered by neighbouring substituents.
 Conformations with their bulky substituents in equatorial positions are favoured.
 In glucose, the α-anomer has the –OH group of C-1 trans to the –CH2OH substituent (axial and down), whereas
the β-anomer has the –OH group of C-1 cis to the –CH2OH substituent (equatorial and up).
 For pyranoses, ring conformations can also spontaneously invert into two chair conformations—the 4C1‐chair or
1
C4‐chair conformations—which switches equatorial groups to axial groups and vice versa at each position.
 The lowest energy conformation is one that places as many bulky hydroxyls in the equatorial position as
possible. For most pyranoses, the 4C1‐chair is thus the preferred conformation.
o Draw the chair forms of α- and β-D Glucose
o List some of the important monosacharides (D and L family of aldoses and ketoses) and derived
monosaccharides as per their carbonyl carbon type and number of carbon atoms and their
occurance in plants.