Greek sakcharon = sugar

Carbohydrates polyhydroxyaldehydes or polyhydroxyketones of formula (CH2O)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: Cu3+ (blue) Cu2+ (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 CO2 + 6 H2O
sunlight
(+)-glucose

C6H12O6 + 6 O2
(+)-glucose

starch or cellulose

respiration
C6H12O6 + 6 O2

6 CO2 + 6 H2O + energy

Animals
plant starch

(+)-glucose

(+)-glucose

glycogen

glycogen

(+)-glucose

(+)-glucose

fats or aminoacids

respiration
(+)-glucose + 6 O2

6 CO2 + 6 H2O + energy

glyceraldehyde
an aldotriose

CHO
H
OH
CH2OH
D-(+)-glyceraldehyde

*
CH2CHCH O
OH OH
CHO
HO
H
CH2OH
L-(-)-glyceraldehyde

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

aldotetroses

* *
CH2CHCHCH O
OH OHOH

CHO
H
OH
H
OH
CH2OH

CHO
HO
H
HO
H
CH2OH

D-erythrose

L-erythrose

CHO
H
OH
HO
H
CH2OH

CHO
HO
H
H
OH
CH2OH

L-threose

D-threose

(+)-glucose? An aldohexose
Emil Fischer (1902)

* * * *
CH2CHCHCHCHCH O
OH OHOHOHOH

Four chiral centers, 24 = 16 stereoisomers

CHO
OH?

CH2OH

H
H
H
H

CHO
OH
OH
OH
OH
CH2OH

HO
HO
H
H

CHO
H
H
OH
OH
CH2OH

H
HO
HO
H

CHO
OH
H
H
OH
CH2OH

HO
HO
HO
HO

CHO
H
H
H
H
CH2OH

H
H
HO
HO

CHO
OH
OH
H
H
CH2OH

HO
H
H
HO

CHO
H
OH
OH
H
CH2OH

HO
H
H
H

CHO
H
OH
OH
OH
CH2OH

H
H
HO
H

CHO
OH
OH
H
OH
CH2OH

HO
HO
HO
H

CHO
H
H
H
OH
CH2OH

H
HO
HO
HO

CHO
OH
H
H
H
CH2OH

HO
HO
H
HO

CHO
H
H
OH
H
CH2OH

H
H
H
HO

CHO
OH
OH
OH
H
CH2OH

H
HO
H
H

CHO
OH
H
OH
OH
CH2OH

HO
H
HO
H

CHO
H
OH
H
OH
CH2OH

HO
H
HO
HO

CHO
H
OH
H
H
CH2OH

H
HO
H
HO

CHO
OH
H
OH
H
CH2OH

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
H
OH
CH2OH

Br2
H2O

CO2H
H
OH
H
OH
CH2OH
Ca2+

CHO
H
OH
CH2OH
D-(+)-glyceraldehyde

H2O2
Fe3+

CO2
H
OH
H
OH
CH2OH

Kiliani-Fischer synthesis. A series of reactions that extends the

carbon chain in a carbohydrate by one carbon and one chiral
center.

CHO
HCN
H
OH
CH2OH

C N
C N
COOH
COOH
HO
H
H
OH
H+,H2O H
OH HO
H
+ H
OH
H
OH
H
OH H
OH
CH2OH
CH2OH
CH2OH
CH2OH

CHO
H
OH
H
OH
CH2OH

Na(Hg)

O C
H
OH
H
OH
H2C
O
lactone

diastereomers
separable

-H2O

Epimers stereoisomers that differ only in configuration about

one chiral center.

H
HO
H
H

CHO
OH
H
OH
OH
CH2OH

D-glucose

HO
HO
H
H

CHO
H
H
OH
OH
CH2OH

D-mannose
epimers

H
HO
H
H

CHO
OH
H
OH
OH
CH2OH

(+)-glucose

Exists only in solution. There are two

solids:
-glucose m 146o

[] = +112.2

-glucose m 150o [] = +17.5

In water each mutarotates to an

equilibrium with [] = +52.7
(63.6% / 36.4% )

H OH

H
HO
H
H

HO

HO
HO

H
H

OH
OH

CHO
OH
H
OH
OH
CH2OH

H OH
HO
HO

H
OH

OH
H

OH
H

beta-(+)-glucose

CH2OH
O
OH

H
H

alpha-(+)-glucose

HO

OH

CH2OH
O
OH

OH

H
H

OH
H

OH

OH

Addition of alcohols to aldehydes/ketones:

O
C

+ R'OH

OH
R C H
OR'
hemiacetal
geminal
ether/alcohol
reducing!

OR'
R C H
OR'
acetal
geminal
diether
non-reducing!

H OH
HO

HO
HO

H
H

OH
H

OH

H
HO
H
H

CHO
OH
H
OH
OH
CH2OH

H OH
HO

HO
HO

H
H

H
OH
OH

nucleophilic addition of -OH on carbon 5 to the aldehyde functional group

H OH
H
HO
H
H

CHO
OH
H
OH
OH
CH2OH

H
HO
H
HOH2C

CH O
OH
H
OH
H
OH

rotate C-5 OH to rear

HO

HO
HO

H
H

H
OH
OH

H OH
HO

HO
HO

H
H

OH
H

OH

H OH

H OH

HO

HO
HO

H
H
alpha
O

4H-Pyran

OH
OH

HO

HO
HO

H
H

hemiacetal

OH
H
beta

D-glucopyranoses

OH

H
HOHO
O
HO
H
H
OH
OH
H

HOHO
O
HO
H
H
H
OH
H

alpha furanose form

beta furanose form

D-glucofuranoses
O
furan

OH

H OH

H OH

HO

HO
HO

H
H

OH
OH

HO

HO
HO

alpha

H
H

OH
H

OH

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

CH2OHO
H
H
OH

CH2OH
OH
H

OH

alpha-D-fructofuranose

CH2OH
O
HO
H
H
OH
H
OH
CH2OH
D-fructose

CH2OHO
H
H
OH

OH
OH
H

CH2OH

beta-D-fructofuranose

H OH
HO

HO
HO

H
H

OH
H

CH3OH
OH

HCl

acetal

H OH
HO

HO
HO

H
H

OH
H

OCH3

methyl beta-D-glucoside
(glucoside - glucose acetal)
non-reducing, does not mutarotate

Disaccharides:
(+)-maltose

malt sugar
two glucose units (alpha)

(+)-cellobiose
two glucose units (beta)
(+)-lactose

milk sugar
galactose & glucose

(+)-sucrose

table sugar
glucose & fructose

H OH
HO

HO
HO

H
H

OH

H OH
HO

HO

HO

HO
HO

H
H

H
H

(+)-maltose
H OH

two glucose units

alpha C-1 to C-4

OH
H

OH
reducing sugar

H OH

O
OH HO
H

HO
H
H

(+)-cellobiose

OH
H

OH

two glucose units

beta C-1 to C-4

reducing sugar

HO OH

H OH

HO

H
HO

H
H

O
OH HO
H

galactose beta C-1

to C-4 glucose

HO
H

H
(+)-lactose

OH
H

OH
reducing sugar

H OH
HO

HO
HO

H
H

OH

acetal
non-reducing

H
OH
O
H OH

CH2OH

HO

(+)-sucrose

glucose alpha C-1

to beta C1 fructose

Polysaccharides
starch
cellulose
Starch

20% amylose (water soluble)

80% amylopectin (water insoluble)
amylose + H2O (+)-maltose
(+)-maltose + H2O (+)-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

Amylopectin + H2O (+)-maltose

(+)-maltose + H2O (+)-glucose
Also a polyglucose, but branched every 20-25 units:

O
O

O
O

O
O

O
O
O

O
O
O

O
O
CH2
O

O
O

O
O

O
O

Cellulose is a polyglucose with a beta-linkage:

O O
O O

O O
O O
O O
O O
O O
O O