Chapter 12 Carbohydrates

Carbohydrates Synthesized by plants using sunlight to convert CO2 and H2O to glucose and O2. Polymers include starch and cellulose. Starch is storage unit for solar energy. Most sugars have formula Cn(H2O)n, “hydrate of carbon.” Chapter 13

Classification of Carbohydrates Monosaccharides or simple sugars polyhydroxyaldehydes or aldoses polyhydroxyketones or ketoses Disaccharides can be hydrolyzed to two monosaccharides. Polysaccharides hydrolyze to many monosaccharide units. E.g., starch and cellulose have > 1000 glucose units. Chapter 12

Monosaccharides Classified by: aldose or ketose number of carbons in chain configuration of chiral carbon farthest from the carbonyl group fructose, a D-ketohexose => glucose, a D-aldohexose Chapter 12

D and L Sugars D sugars can be degraded to the dextrorotatory (+) form of glyceraldehyde. L sugars can be degraded to the levorotatory (-) form of glyceraldehyde. Chapter 12

The D Aldose Family Chapter 23

Epimers Sugars that differ only in their stereochemistry at a single carbon. Chapter 12

Cyclic Structure for Glucose Glucose cyclic hemiacetal formed by reaction of -CHO with -OH on C5. D-glucopyranose Chapter 12

Cyclic Structure for Fructose Cyclic hemiacetal formed by reaction of C=O at C2 with -OH at C5. D-fructofuranose Chapter 12

Anomers Chapter 12

Mutarotation Glucose also called dextrose; dextrorotatory. Chapter 12

Epimerization In base, H on C2 may be removed to form enolate ion. Reprotonation may change the stereochemistry of C2. Chapter 12

Reduction of Simple Sugars C=O of aldoses or ketoses can be reduced to C-OH by NaBH4 or H2/Ni. Name the sugar alcohol by adding -itol to the root name of the sugar. Reduction of D-glucose produces D-glucitol, commonly called D-sorbitol. Reduction of D-fructose produces a mixture of D-glucitol and D-mannitol. Chapter 12

Oxidation by Nitric Acid Nitric acid oxidizes the aldehyde and the terminal alcohol; forms aldaric acid. Chapter 12

Oxidation by Tollens Reagent Tollens reagent reacts with aldehyde, but the base promotes enediol rearrangements, so ketoses react too. Sugars that give a silver mirror with Tollens are called reducing sugars. Chapter 12

Nonreducing Sugars Glycosides are acetals, stable in base, so they do not react with Tollens reagent. Disaccharides and polysaccharides are also acetals, nonreducing sugars. Chapter 23

Formation of Glycosides React the sugar with alcohol in acid. Since the open chain sugar is in equilibrium with its - and -hemiacetal, both anomers of the acetal are formed. Aglycone is the term used for the group bonded to the anomeric carbon. Chapter 23

Ether Formation Sugars are difficult to recrystallize from water because of their high solubility. Convert all -OH groups to -OR, using a modified Williamson synthesis, after converting sugar to acetal, stable in base. Chapter 23

Ester Formation Acetic anhydride with pyridine catalyst converts all the oxygens to acetate esters. Chapter 12

Osazone Formation Both C1 and C2 react with phenylhydrazine. Chapter 23

Kiliani-Fischer Synthesis This process lengthens the aldose chain. A mixture of C2 epimers is formed. Chapter 12

Fischer’s Proof Emil Fischer determined the configuration around each chiral carbon in D-glucose in 1891, using Ruff degradation and oxidation reactions. He assumed that the -OH is on the right in the Fischer projection for D-glyceraldehyde. This guess turned out to be correct! Chapter 12

Disaccharides Three naturally occurring glycosidic linkages: 1-4’ link: The anomeric carbon is bonded to oxygen on C4 of second sugar. 1-6’ link: The anomeric carbon is bonded to oxygen on C6 of second sugar. 1-1’ link: The anomeric carbons of the two sugars are bonded through an oxygen. Chapter 12

Cellobiose Two glucose units linked 1-4’. Disaccharide of cellulose. A mutarotating, reducing sugar. Chapter 12

Maltose Two glucose units linked 1-4’. Chapter 12

Lactose Galactose + glucose linked 1-4’. “Milk sugar.” Chapter 12

Sucrose Glucose + fructose, linked 1-1’ Nonreducing sugar Chapter 12

Cellulose Polymer of D-glucose, found in plants. Mammals lack the -glycosidase enzyme. Chapter 12

Amylose Soluble starch, polymer of D-glucose. Starch-iodide complex, deep blue. Chapter 12

Amylopectin Branched, insoluble fraction of starch. Chapter 12

Glycogen Glucose polymer, similar to amylopectin, but even more highly branched. Energy storage in muscle tissue and liver. The many branched ends provide a quick means of putting glucose into the blood. Chapter 12

REVIEW

In the Fischer projection of D-(+)-glyceraldehyde, the hydroxyl group on the asymmetric carbon center is: A) on the bottom B) on the top C) at the left D) at the right E) present as a hemiacetal

In the Fischer projection of D-(+)-glyceraldehyde, the hydroxyl group on the asymmetric carbon center is: A) on the bottom B) on the top C) at the left D) at the right E) present as a hemiacetal

All naturally occurring sugars can be degraded to: A) D-(-)-glyceraldehyde B) D-(+)-glyceraldehyde C) L-(-)-glyceraldehyde D) L-(+)-glyceraldehyde E) none of the above

All naturally occurring sugars can be degraded to: A) D-(-)-glyceraldehyde B) D-(+)-glyceraldehyde C) L-(-)-glyceraldehyde D) L-(+)-glyceraldehyde E) none of the above

All chiral D-sugars rotate plane-polarized light: A) clockwise. B) counterclockwise. C) +20.0°. D) in a direction that cannot be predicted but must be determined experimentally. E) since they are optically inactive.

All chiral D-sugars rotate plane-polarized light: A) clockwise. B) counterclockwise. C) +20.0°. D) in a direction that cannot be predicted but must be determined experimentally. E) since they are optically inactive.

The structure of D-arabinose is shown below The structure of D-arabinose is shown below. Which of the following correctly describes the configurations of the asymmetric carbons in D-arabinose? A) 2S, 3R, 4R B) 2R, 3S, 4S C) 2S, 3R, 4S D) 2R, 3S, 4R E) 2S, 3S, 4R

The structure of D-arabinose is shown below The structure of D-arabinose is shown below. Which of the following correctly describes the configurations of the asymmetric carbons in D-arabinose? A) 2S, 3R, 4R B) 2R, 3S, 4S C) 2S, 3R, 4S D) 2R, 3S, 4R E) 2S, 3S, 4R

Stereoisomeric aldohexoses that differ in configuration at only a single carbon are: A) meso compounds. B) threo sugars. C) enantiomers. D) constitutional isomers. E) epimers.

Stereoisomeric aldohexoses that differ in configuration at only a single carbon are: A) meso compounds. B) threo sugars. C) enantiomers. D) constitutional isomers. E) epimers.

Draw the Haworth structure of β-D-glucopyranose.

Draw the Haworth structure of β-D-glucopyranose. Answer:

Anomers of D-glucopyranose differ in their stereochemistry at: A) C5 B) C4 C) C3 D) C2 E) C1

Anomers of D-glucopyranose differ in their stereochemistry at: A) C5 B) C4 C) C3 D) C2 E) C1

The α and β anomers of a D-glucopyranose are related as: A) enantiomers. B) meso compounds. C) structural isomers. D) epimers. E) disaccharides.

The α and β anomers of a D-glucopyranose are related as: A) enantiomers. B) meso compounds. C) structural isomers. D) epimers. E) disaccharides.

Name . a. a-D-Fructopyranose b. b-D-Fructopyranose c. a-D-Fructofuranose d. b-D-Fructofuranose

a. a-D-Fructopyranose b. b-D-Fructopyranose c. a-D-Fructofuranose d. b-D-Fructofuranose The cyclic structure comes from D-fructose and has a five-membered ring (furan). The OH on the far-right carbon is pointed down (a).

List the aldose carbon(s) that are oxidized with HNO3. a. The first carbon b. The second carbon c. The last carbon d. The second to the last carbon e. The first and last carbon

a. The first carbon b. The second carbon c. The last carbon d. The second to the last carbon e. The first and last carbon Nitric acid oxidizes an aldehyde and –CH2OH.

List the aldose carbon(s) that are oxidized with Tollens reagent. a. The first carbon b. The second carbon c. The last carbon d. The second to the last carbon e. The first and last carbon

a. The first carbon b. The second carbon c. The last carbon d. The second to the last carbon e. The first and last carbon Tollens reagent oxidizes an aldehyde.

List the sugar hydroxyl(s) that are methylated with CH3I and AgI. a. On Carbon 1 b. On Carbon 2 c. On CH2OHs only d. On all carbons e. None of them

a. On Carbon 1 b. On Carbon 2 c. On CH2OHs only d. On all carbons e. None of them CH3I and AgI methylate all hydroxyl groups.

List the sugar hydroxyl(s) that are esterified with anhydrides. a. On Carbon 1 b. On Carbon 2 c. On CH2OHs only d. On all carbons e. None of them

a. On Carbon 1 b. On Carbon 2 c. On CH2OHs only d. On all carbons e. None of them All hydroxyl groups are esterified.

Explain what happens in the Ruff degradation. a. The aldose chain is shortened by one carbon. b. The aldose chain is lengthened by one carbon. c. Two aldose chains combine. d. Branching occurs on the aldose chain.

a. The aldose chain is shortened by one carbon. b. The aldose chain is lengthened by one carbon. c. Two aldose chains combine. d. Branching occurs on the aldose chain. The Ruff degradation shortens the aldose chain by one carbon.

Explain what happens in the Kiliani–Fischer synthesis. a. The aldose chain is shortened by one carbon. b. The aldose chain is lengthened by one carbon. c. Two aldose chains combine. d. Branching occurs on the aldose chain.

a. The aldose chain is shortened by one carbon. b. The aldose chain is lengthened by one carbon. c. Two aldose chains combine. d. Branching occurs on the aldose chain. The Kiliani–Fischer synthesis lengthens the aldose chain by one carbon.

Describe amylose. a. a-1,4’ Glycosidic linkages b. Water soluble c. Polymer of a-D-glucopyranose d. All of the above e. None of the above

a. a-1,4’ Glycosidic linkages b. Water soluble c. Polymer of a-D-glucopyranose d. All of the above e. None of the above

End of Chapter 12