Greek sakcharon = sugar

Carbohydrates polyhydroxyaldehydes or polyhydroxy-

ketones of formula (CH
2
O)
n
, or compounds that can be
hydrolyzed to them. (aka sugars or saccharides)
Monosaccharides carbohydrates that cannot be hydrolyzed
to simpler carbohydrates; eg. Glucose or fructose.
Disaccharides carbohydrates that can be hydrolyzed into
two monosaccharide units; eg. Sucrose, which is hydrolyzed
into glucose and fructose.
Oligosaccharides carbohydrates that can be hydrolyzed into
a few monosaccharide units.
Polysaccharides carbohydrates that are are polymeric
sugars; eg Starch or cellulose.
Aldose polyhydroxyaldehyde, eg glucose
Ketose polyhydroxyketone, eg fructose
Triose, tetrose, pentose, hexose, etc. carbohydrates that
contain three, four, five, six, etc. carbons per molecule
(usually five or six); eg. Aldohexose, ketopentose, etc.
Reducing sugar a carbohydrate that is oxidized by Tollens,
Fehlings or Benedicts solution.
Tollens: Ag
+
Ag (silver mirror)
Fehlings or Benedicts: Cu
3+
(blue) Cu
2+
(red ppt)
These are reactions of aldehydes and alpha-hydroxyketones.
All monosaccharides (both aldoses and ketoses) and most
*

disaccharides are reducing sugars.
*
Sucrose (table sugar), a disaccharide, is not a reducing sugar.

Glucose (a monosaccharide)
Plants:
photosynthesis
chlorophyll
6 CO
2
+ 6 H
2
O C
6
H
12
O
6
+ 6 O
2

sunlight (+)-glucose

(+)-glucose starch or cellulose


respiration

C
6
H
12
O
6
+ 6 O
2
6 CO
2
+ 6 H
2
O + energy
Animals
plant starch (+)-glucose
(+)-glucose glycogen
glycogen (+)-glucose
(+)-glucose fats or aminoacids
respiration
(+)-glucose + 6 O
2
6 CO
2
+ 6 H
2
O + energy
OH
CHO
H
CH
2
OH
H
CHO
HO
CH
2
OH
D-(+)-glyceraldehyde
L-(-)-glyceraldehyde
glyceraldehyde
an aldotriose
CH
2
CHCH O
OH OH
*
D & L are used to relate configuration of the chiral center
most removed from the reducing group ( C=O ). If the -OH
is on the right in the Fischer projection, then it is D, if the -OH
is on the left, then it is L
CHO
H OH
CH
2
OH
H OH
aldotetroses
CH
2
CHCHCH O
OH OHOH
* *
CHO
HO H
CH
2
OH
HO H
CHO
H OH
CH
2
OH
HO H
CHO
HO H
CH
2
OH
H OH
D-erythrose
L-erythrose
L-threose D-threose
(+)-glucose? An aldohexose
Emil Fischer (1902)
Four chiral centers, 2
4
= 16 stereoisomers
CHO
CH
2
OH
OH?
CH
2
CHCHCHCHCH O
OH OHOHOHOH
* *
*
*
CHO
OH H
OH H
OH H
OH H
CH
2
OH
CHO
H HO
OH H
OH H
OH H
CH
2
OH
CHO
OH H
H HO
OH H
OH H
CH
2
OH
CHO
H HO
H HO
OH H
OH H
CH
2
OH
CHO
OH H
OH H
H HO
OH H
CH
2
OH
CHO
H HO
OH H
H HO
OH H
CH
2
OH
CHO
OH H
H HO
H HO
OH H
CH
2
OH
CHO
H HO
H HO
H HO
OH H
CH
2
OH
CHO
HO H
HO H
HO H
HO H
CH
2
OH
CHO
H OH
HO H
HO H
HO H
CH
2
OH
CHO
HO H
H OH
HO H
HO H
CH
2
OH
CHO
H OH
H OH
HO H
HO H
CH
2
OH
CHO
HO H
HO H
H OH
HO H
CH
2
OH
CHO
H OH
HO H
H OH
HO H
CH
2
OH
CHO
HO H
H OH
H OH
HO H
CH
2
OH
CHO
H OH
H OH
H OH
HO H
CH
2
OH
Ruff degradation a series of reactions that removes the
reducing carbon ( C=O ) from a sugar and decreases the
number of chiral centers by one; used to relate configuration.
CHO
H OH
CH
2
OH
H OH
CO
2
H
H OH
CH
2
OH
H OH
Br
2
H
2
O
CO
2
H OH
CH
2
OH
H OH
Ca
2+
H
2
O
2
Fe
3
+
CHO
CH
2
OH
H OH
D-(+)-glyceraldehyde
Kiliani-Fischer synthesis. A series of reactions that extends the
carbon chain in a carbohydrate by one carbon and one chiral
center.
CHO
H OH
CH
2
OH
HCN
C
H OH
CH
2
OH
H OH
C
HO H
CH
2
OH
H OH
+
N
N
H
+
,H
2
O
COOH
H OH
CH
2
OH
H OH
COOH
HO H
CH
2
OH
H OH
diastereomers
separable
C
H OH
H
2
C
H OH
O
O
lactone
Na(Hg)
CHO
H OH
CH
2
OH
H OH
-H
2
O
Epimers stereoisomers that differ only in configuration about
one chiral center.
CHO
OH H
H HO
OH H
OH H
CH
2
OH
D-glucose
CHO
H HO
H HO
OH H
OH H
CH
2
OH
D-mannose
epimers
CHO
OH H
H HO
OH H
OH H
CH
2
OH
(+)-glucose
Exists only in solution. There are two
solids:
-glucose m 146
o
[] = +112.2
-glucose m 150
o
[] = +17.5

In water each mutarotates to an
equilibrium with [] = +52.7
(63.6% / 36.4% )
CHO
OH H
H HO
OH H
OH H
CH
2
OH
O
H
HO
H
HO
H
OH
OH
H
H
OH
O
H
HO
H
HO
H
H
OH
H
OH
OH
alpha-(+)-glucose
beta-(+)-glucose
O
H
OH
OH
H
H
OH H
OH
CH
2
OH
O
H
OH
H
OH
H
OH H
OH
CH
2
OH
R
C
H
O
+ R'OH
R C H
OH
OR'
R C H
OR'
OR'
hemiacetal
geminal
ether/alcohol
reducing!
acetal
geminal
diether
non-reducing!
Addition of alcohols to aldehydes/ketones:
CHO
OH H
H HO
OH H
OH H
CH
2
OH
O
H
HO
H
HO
H
OH
OH
H
H
OH
O
H
HO
H
HO
H
H
OH
H
OH
OH
nucleophilic addition of -OH on carbon 5 to the aldehyde functional group
CHO
OH H
H HO
OH H
OH H
CH
2
OH
CH
OH H
H HO
OH H
H HOH
2
C
OH
O
H
HO
H
HO
H
OH
OH
H
H
OH
O
O
H
HO
H
HO
H
H
OH
H
OH
OH

rotate C-5 OH to rear

O
H
HO
H
HO
H
H
OH
H
OH
OH
O
H
HO
H
HO
H
OH
OH
H
H
OH
hemiacetal
4H-Pyran
O
D-glucopyranoses
alpha
beta
OH
H
H
H
OH
HO H
O
H
HO
HO
H
OH
H
H
OH
HO H
O
H
HO
HO
O
furan
alpha furanose form beta furanose form
D-glucofuranoses
O
H
HO
H
HO
H
H
OH
H
OH
OH
O
H
HO
H
HO
H
OH
OH
H
H
OH
alpha
beta
anomers - epimers at C-1
chair conformations - alpha has one group axial
beta has all groups equatorial
mutarotation in solution to 63.6% beta/36.4% alpha
CH
2
OH
O
H HO
OH H
OH H
CH
2
OH
D-fructose
CH
2
OH
OH
H
CH
2
OH
OH
H
H OH
O
beta-D-fructofuranose
OH
CH
2
OH
H
CH
2
OH
OH
H
H OH
O
alpha-D-fructofuranose
O
H
HO
H
HO
H
H
OH
H
OH
OH
CH
3
OH
HCl
O
H
HO
H
HO
H
H
OH
H
OCH
3
OH
acetal
(glucoside - glucose acetal)
non-reducing, does not muta-
rotate
methyl beta-D-glucoside
Disaccharides:
(+)-maltose malt sugar
two glucose units (alpha)
(+)-cellobiose
two glucose units (beta)
(+)-lactose milk sugar
galactose & glucose
(+)-sucrose table sugar
glucose & fructose
(+)-maltose
O
H
H
HO
H
H
OH
H
OH
OH
O
H
HO
H
HO
H
OH
H
H
OH
O
two glucose units
alpha C-1 to C-4
reducing sugar
O
H
HO
H
HO
H
H
OH
H
OH
O
H
O
H
HO
H
H
OH
H
OH
OH
(+)-cellobiose
two glucose units
beta C-1 to C-4
reducing sugar
O
H
HO
H
HO
H
OH
H
H
OH
glucose alpha C-1
to beta C1 fructose
O
HO
H
H
HO
H
H
OH
H
OH
O
H
O
H
HO
H
H
OH
H
OH
OH
galactose beta C-1
to C-4 glucose
reducing sugar (+)-lactose
O
O
C
H
2
O
H
CH
2
OH
H
H
OH
HO
H
(+)-sucrose
acetal
non-reducing
Polysaccharides
starch
cellulose
Starch 20% amylose (water soluble)
80% amylopectin (water insoluble)
amylose + H
2
O (+)-maltose
(+)-maltose + H
2
O (+)-glucose
starch is a poly glucose (alpha-glucoside to C-4)
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
CH
2
O
Amylopectin + H
2
O (+)-maltose
(+)-maltose + H
2
O (+)-glucose
Also a polyglucose, but branched every 20-25 units:

Cellulose is a polyglucose with a beta-linkage:
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O