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 glycogen (+)-glucose respiration (+)-glucose + 6 O2 6 CO2 + 6 H2O + energy (+)-glucose glycogen (+)-glucose fats or aminoacids

glyceraldehyde an aldotriose

* CH2CHCH O OH OH

CHO H OH CH2OH
D-(+)-glyceraldehyde

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 HO H HO H CH2OH L-erythrose

CHO H OH H OH CH2OH D-erythrose

CHO H OH HO H CH2OH L-threose

CHO HO H H OH CH2OH 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 CHO H H OH OH CH2OH

HO HO HO HO

CHO H H H H CH2OH CHO OH OH H H CH2OH

HO H H H

CHO H OH OH OH CH2OH CHO OH OH H OH CH2OH

H HO HO HO

CHO OH H H H CH2OH CHO H H OH H CH2OH

H HO H H

CHO OH H OH OH CH2OH CHO H OH H OH CH2OH

HO H HO HO

CHO H OH H H CH2OH CHO OH H OH H CH2OH

HO HO H H

H H HO HO

H H HO H

HO HO H HO

HO H HO H

H HO H HO

H HO HO H

CHO OH H H OH CH2OH

HO H H HO

CHO H OH OH H CH2OH

HO HO HO H

CHO H H H OH CH2OH

H H H HO

CHO OH OH 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+ CO2 H OH H OH CH2OH

CHO H OH CH2OH D-(+)-glyceraldehyde

H2O2 Fe3+

Kiliani-Fischer synthesis. A series of reactions that extends the carbon chain in a carbohydrate by one carbon and one chiral center.
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 diastereomers separable Na(Hg) O C H OH H OH H2C O lactone

CHO HCN H OH CH2OH

CHO H OH H OH CH2OH

-H2O

Epimers stereoisomers that differ only in configuration about one chiral center.
CHO OH H OH OH CH2OH CHO H H OH OH CH2OH

H HO H H

HO HO H H

D-glucose epimers

D-mannose

H HO H H

CHO OH H OH OH CH2OH

Exists only in solution. There are two solids:

-glucose m 146o [] = +112.2 -glucose m 150o [] = +17.5

(+)-glucose

In water each mutarotates to an equilibrium with [] = +52.7 (63.6% / 36.4% )

H OH HO HO H HO H OH OH H

H HO H H

CHO OH H OH OH CH2OH

H OH HO HO H HO H OH H OH

alpha-(+)-glucose

beta-(+)-glucose

H OH

CH2OH O OH H H

H OH

H OH

CH2OH O 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 H HO H OH H OH

H HO H H

CHO OH H OH OH CH2OH

H OH HO HO H HO 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 CH O OH H OH H OH HO HO H H OH HO HO H HO H OH H OH HO H H OH OH

H HO H HOH2C

rotate C-5 OH to rear

H OH HO HO H alpha O HO H OH OH H

H OH HO HO H HO H OH H beta OH

hemiacetal

D-glucopyranoses

4H-Pyran

H HOHO O HO H H OH OH H alpha furanose form

HOHO O HO H H H OH H

OH

beta furanose form

D-glucofuranoses O furan

H OH HO HO H alpha HO H OH OH H

H OH HO HO H HO H OH H beta OH

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

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

CH2OHO H H OH

OH OH H CH2OH

alpha-D-fructofuranose

beta-D-fructofuranose

H OH HO HO H HO H OH H OH CH3OH HCl

acetal H OH HO HO H HO 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 table sugar glucose & fructose

(+)-sucrose

H OH HO HO H O HO H H HO H OH H H OH HO OH H OH reducing sugar two glucose units alpha C-1 to C-4

(+)-maltose H OH HO HO H HO H

H OH HO H H OH H OH two glucose units beta C-1 to C-4

O OH HO H

(+)-cellobiose

reducing sugar

HO OH H HO H HO H

H OH HO H H OH H OH

O OH HO H

galactose beta C-1 to C-4 glucose

(+)-lactose H OH HO HO H acetal non-reducing HO H OH H

reducing sugar

CH2OH

OH O H OH HO H

glucose alpha C-1 to beta C1 fructose

CH2OH

(+)-sucrose

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 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 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