Chapter 7: Outline

Monosaccharides Monosaccharide stereoisomers Cyclic structures Reactions Examples and derivatives Di and oligosaccharides Polysaccharides Homo and heteropolysaccharides Glycoconjugates
7P1-1

Originally, carbohydrates were those compounds having the formula Cn(H2O)n. Only monosaccharides or simple sugars fit the formula. As more complex carbohydrates were discovered, the term came to mean compounds associated with polyhydroxy aldehydes and ketones. 7P1-2

7.1 Monosaccharides
polyhydroxy Number of carbons 3=triose 4=tetrose 5=pentose 6=hexose

Aldehydes are aldoses

Ketones are ketoses

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Monosaccharides: generic names

The generic name for a simple sugar begins with the carbonyl prefix aldo or keto and ends with the term for the number of carbons. An aldose with three carbons is called an aldotriose. A ketose with three carbons is a ketotriose. What is the name for a six carbon aldehyde sugar? aldohexose What is the name for a five carbon ketone sugar? ketopentose 7P1-4

Dihydroxyacetone
Dihydroxyacetone

CH2OH C O CH2OH
Is a ketotriose

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Glyceraldehyde
Glyceraldehyde Is an aldotriose

O C

H C OH CH2OH
Glyceraldehyde exists in two stereoisomeric forms because the starred carbon is a stereocenter: it has four different groups attached.
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The stereoisomers of glyceraldehyde are designated D or L. The D isomer has the OH on the stereocenter to the right. The L isomer has the OH on the left .

O C
stereocenter

O C

H C OH
the D isomer

HO C H
the L isomer

CH2OH

CH2OH
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Glyceraldehyde: 3
The stereoisomeric forms of glyceraldehyde are enantiomers: nonsuperimposable mirror image molecules. Perspective drawings of the two enantiomers of glyceraldehyde are on the next slide. A stereo view is on slide 11. Remember, barred bonds ( ) recede behind the plane of the screen and wedge ( ) bonds project in front of the plane. 7P1-8

Perspective View

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View with blue lens on the left eye.

Carbonyl group

H atom

OH group

CH2OH group Stereoscopic view of glyceraldehyde

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Fischer Projections
In a Fischer projection, the sugar molecule is oriented so that the most O oxidized carbon is to the top. The stereocenter carbons are arranged so H that the groups not part of H the main chain project horizontally toward the viewer. The molecule is in the all eclipsed form.

C C OH C OH CH2OH
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Monosaccharides are drawn in Fischer projections with the most oxidized carbon closest to the top. The carbons are numbered from the top. If the the stereocenter with the highest number has the OH to the right, the sugar is D. If the OH is to the left, the sugar is L. Most common sugars are in the D form. Note: Fisher projections represent an all eclipsed conformation.

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CH2OH H 2 C O 1 C H 2 C OH HO 3 C H H 3 C OH H 4 C OH H 4 C OH H 5 C OH 5 CH OH 6 CH OH 2 2 D-ribose D-fructose an aldopentose a ketohexose O

1
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CHO

CHO

OH

OH

HO C H H C OH H C OH CH2OH

HO C H

HO C H
H C OH CH2OH

D-glucose D-galactose an aldohexose an aldohexose These diastereomers are also epimers, they differ in configuration at only one stereo7P1-14 center (colored dot).

Cyclic forms for sugars

Most simple sugars of four or more carbons exist in the cyclic (hemiacetal or hemiketal) form. A hydroxy group in the sugar reacts with the carbonyl group. The new OH bearing carbon is now a stereo center and is called an anomeric carbon. If the OH on the ring is up the carbon is F, if the OH is down it is E.
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Cyclic forms for sugars-2

Fischer projections for E D glucose

H C OH HO C H CO H C OH H C OH C OH HO C H O HO C H O CH H C OH H C OH C OH HC HC C OH CH2OH CH2OH CH2OH D-glucose E D-glucose F D-glucose H H HO H H

cyclic form cyclic form
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Cyclic forms for sugars-3 Haworth

1. Draw a five- or six-membered ring O O
pyranose form furanose form 2. Anomeric C to right of O. Place OH up or down. Left on Fischer, up on ring.

3. In D- sugars, the last C is always up.

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Cyclic forms for sugars-4 Haworth

CH2OH Anomeric C F-OH C O HO C H HO CH2 O OH H C OH HO CH2OH H C OH OH CH2OH F-D-fructofuranose D-fructose + E isomer

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Cyclic forms for sugars-5 Glucose

CH2OH arrows show O H E form H electron movement H (alpha) OH H CH2OH HO O H OH H H OH Pyranose H H OH H O CH2OH ring form HO OOH H H OH H F form H OH HO H (beta) H OH 7P1-19

Cyclic forms for sugars-6

The alpha and beta forms of cyclic sugars are said to be anomers. They differ in configuration about the hemiacetal or hemiketal carbon.

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Cyclic forms for sugars-7

Ribose also exists mainly in the cyclic form.
arrows show electron movement
CH2OH O H H H OH OH H H O H OH

F D-ribose F D-ribofuranose (furanose ring form) CH2OH O H O

H H H OH
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E D-glucose: the chair conformer

H HO
4

H CH2OH O
6 5 2 3

HO H H

H
1

OH OH
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Four of the five bulky groups (OH and CH2OH on C 2,3,4,5) on the ring are in the more stable equitorial positions!

Oxidation of Monosaccharides
Aldoses react with Tollens reagent (Ag(NH3)2+) to give a lactone (cyclic ester). The silver ion plates out as a mirror. + Ag(mirror)

CH2OH O H H + H Ag(NH3)2 H OH H Cu2+ HO HO OH H OH

CH2OH O H OH H H OH

+ Cu2O (red-orange) Benedicts reagent (a blue copper ion solution) also gives a lactone. The blue color fades as reaction occurs.
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Oxidation of Monosaccharides-2 Aldehyde oxidn aldonic acid

CHO C OH CH C OH C OH COOH H HO H H COOH C OH CH C OH C OH CH2OH

H HO H H

D-gluconic acid

Term CH2OH oxidn uronic acid

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D-glucuronic acid

Oxidation of Monosaccharides-3
Aldehyde + term CH2OH oxidn aldaric acid COOH H C OH HO C H H C OH H C OH COOH
D-glucaric acid

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Reduction of Monosaccharides
The most important reduced sugar is deoxyribose. (In DNA) CH2OH CH2OH O H C OH H C H C OH H C OH H C H HO C H HO C H H C OH H C OH H C OH H C OH CH2OH CH2OH CH2OH D-xylitol D-sorbitol D-deoxyribose When the carbonyl of a sugar is reduced to an alcohol, alditols are produced. The two shown above are used to sweeten nonsugar gum. 7P1-26

Isomerization
H H HO H H CO C OH CH C OH C OH CH2OH H C OH C OH HO C H H C OH H C OH CH2OH

CH2 OH C O HO C H H C OH H C OH CH2OH H HO HO H H CO CH CH C OH C OH CH2OH 7P1-27

Isomerization of monosaccharides occurs through an enediol.

Esters of Monosaccharides
The OH groups of sugars can react with phosphoric acid to give phosphate 2esters.

CH2OPO3 O OH H H OH H HO H H OH

F D-glucose-6-phosphate 7P1-28

Glycosides
The anomeric OH can react with another OH on an alcohol or sugar. Water is lost to form an acetal/ketal

CH2OH H O OH H OH H HO H H OH + CH3 O H

CH2OH H O O CH3 H OH H HO H H OH Acetal + H2O

carbon
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Acetal link: R-O-C-O-R

Important Monosaccharides
CH2 OH O H H H OH H HO OH H OH CH2 OH O HO H H OH H OH H H OH

HOCH2 O OH H HO H CH2OH OH H
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Amino Sugars

CH2 OH CH2 OH O O H H H H H H OH H OH H OH HO OH HO
H
E-D-glucosamine

NH3

N-acetyl-E-D-glucosamine
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NH CH3C O

Amino Sugars-2

O CH3C NH HO

O R

COO

OH N-acetylnuraminic acid sialic acid

H C OH OH R= H C OH CH2OH

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