Carbohydrate Chemistry

Learning Goals:
1. Understand carbohydrate nomenclature.
2. Understand carbohydrate stereochemistry
3. Understand the chemistry/consequences of hemiacetal/hemiketal formation
4. Understand the nomenclature/chemistry of disaccharide formation
I. Nomenclature of Simple Carbohydrates
a. (CH2O)n
b. Monosaccharides: carbonyl function (aldehyde or ketone), 2+ alcohol groups
c. Carbons numbered from carbonyl end
d. Monosaccharides characterized by number of carbons
i. Chiral carbons- 4 different groups attached to a carbon, can have different configurations
1.  optically active
ii. Isomers- same atoms but arranged differently
iii. Epimers- compounds differing only by configuration about a single carbon atom
iv. Enantiomers- isomers that exist as mirror image molecules
1. L and D designate the absolute configuration of the asymmetric C atom farthest from
the aldehyde/ketone group
v. Diastereomers- isomers that differ in configuration of one or more carbons but not in location
of the carbonyl group and are not mirror images
e. –conic acid/conate: aldohexoses in which the C1-carbonyl group is oxidized to –COOH
-uronic acid: aldohexoses in which the C6-CH2OH group has been oxidized to –COO-
reduction of the carbonyl carbon creates a new alcohol group and converts the monosaccharide to a
polyol
II. Cyclization of monosaccharides
a. Open chain forms of sugars cyclize into rings because it is energetically favorable
b. Electronegativity of carbonyl O  nucleophilic attack  hemiacetals/hemiketals (intramolecular)
c. Ring formation generates a new asymmetric carbon from the originally planar carbonyl group 
anomeric carbon (α- OH in down projection, β- OH in up projection)  configurations in equilibrium
with open chain form
d. Stability of ring structures: distribution of groups in equatorial/axial orientations  most large groups
in equatorial positions of chair most favored
e. Saccharides containing free aldehyde groups = reducing sugar
f. Glycosidic bond- anomeric O is covalently bound to an additional functional group, saccharide is
locked into the ring structure, non-reducing sugar
III. Formation of Glycosidic bonds
a. Disaccharides = 2 sugars linked by a glycosidic bond (stereochemistry is critical- enzymes are
specific)
b. Sucrose, lactose, maltose
c. Complex polyssacharides: starch- amylose, amylopectin, cellulose, glycogen
d. Other glycosidic bonds
i. N-glycosidic bond: anomeric carbon of ribose bound to purine/pyrimidine
ii. O-linked glycosidic bond
iii. N-linked glycosidic bond
IV. Non-specific glycosylation of proteins
a. Schiff’s base- formed by reaction of sugars with the side chain primary amine of lysine  Amadori
rearrangement
b. Diabetic patients, extracellular proteins
V. Carbohydrate digestion
a. Important carbohydrates in the diet
b. Digestion of starch/glycogen begins with α-amylase present in salivary/pancreatic juice
(endosaccharidase)
c. Digestion continued by α-glucosidases located on the small intestine wall (also sucrase and lactase)
d. Problems of carbohydrate digestion
i. Lactase definiciency
ii. Lack enzymes to hydrolyze cellulose, raffinose