CHAPTER20

The Organic Chemistry of Carbohydrates

Important Terms

aldaric acid the compound that results when the aldehyde and primary alcohol groups of an
aldose are oxidized to carboxylic acids.

alditoI the compound that results when the carbonyl group of an aldose is reduced to an
alcohol.

aldonic acid the compound that results when the aldehyde group of an aldose is oxidized to a
carboxylic acid. '

aldose a polyhydroxy aldehyde.

•
amino sugar a sugar in which one of the OH groups is replaced by an NH2 group.

anomeric carbon the carbon in a cyclic sugar that is the carbonyl carbon in the straight-chain form.

anomeric effect preference for the axial position by substituents bonded to the anomeric carbon.

anomers two cyclic sugars that differ in configuration only at the carbon that is the carbonyl
carbon in the straight-chain form.

bioorganic compound an organic compound found in a living system.

carbohydrate a sugar, a saccharide. Naturally occurring carbohydrates have the D-configuration.

complex carbohydrate a carbohydrate that contains two or more sugar molecules linked together.

deoxy sugar a sugar in which one of the OH groups has been replaced by a hydrogen.

disaccharide a compound containing two sugar molecules linked together.

enediolrearrangement a base-catalyzed reaction that interconverts monosaccharides.

epimerization changing the configuration of a carbon by removing a proton and then

reprotonating it.

epimers monosaccharides that differ in configuration at only one carbon.

furanose a five-membered ring sugar.

furanoside a five-membered ring glycoside.

glycoprotein a protein that is covalently bonded to an oligosaccharide.

glycoside the acetal of a sugar.

681

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 682 Chapter 20

N-glycoside a glycoside with a nitrogen instead of an oxygen at the glycosidic linkage.

glycosidic bond the bond between the anomeric carbon of a sugar and an alcohol.

a-1,4 '-glycosidic linkage a glycosidic linkage between the C-1 of one sugar and the C-4 of a second sugar
with the oxygen atom at C-1 in the axial position.

a-1,6' -glycosidic linkage a glycosidic linkage between the C-1 of one sugar and the C-6 of a second sugar
with the oxygen atom at C-1 in the axial position.

P-1,4 '-glycosidic linkage a glycosidic linkage between the C-1 of one sugar and the C-4 of a seconq sugar
with the oxygen atom at C-1 in the equatorial position.

Haworth projection a way to show the structure of a sugar in which the five- and six-membered rings
are represented as being flat.

heptose a monosaccharide with seven carbons.

hexose a monosaccharide with six carbons.

ketose a polyhydroxy ketone.

Kiliani-Fischer synthesis a method used to increase the number of carbons in an aldose by one, resulting in
the formation of a pair of C-2 epimers.

molecular recognition the recognition of one molecule by another as a result of specific interactions.

monosaccharide a single sugar molecule.

mutarotation a slow change in optical rotation to an equilibrium value.

nonreducing sugar a sugar that cannot be oxidized by reagents such as Ag+ or Br2 . Nonreducing
sugars are not in equilibrium with the open-chain aldose or ketose.

oligosaccharid~

oxocarbeniumion an ion in which the positive charge is shared by a carbon and an oxygen.

· pentose a monosaccharide with five carbons.

polysaccharide a compound containing 10 or more sugar molecules linked together.

pyranose a six-membered ring sugar.

pyranoside a six-membered ring glycoside.

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 Chapter 20 683

reducing sugar a sugar that can be oxidized by reagents such as Ag+ or Br2 . Reducing sugars are
in equilibrium with the open-chain aldose or ketose forms.

simple carbohydrate a single sugar molecule.

tetrose a monosaccharide with four carbons.

triose a monosaccharide with three carbons.

Wohl degradation a method used to shorten an aldose by one carbon.

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684 Chapter 20

Solutions to Problems

1. n-Ribose is an aldopentose.
n-Sedoheptulose is a ketoheptose.
n-Mannose is an aldohexose.

2. Notice that an L-sugar is the mirror image of a D-sugar.

H"'- ,f'O
c CH20H
I
HO H c=o

HO
H OH
H HO
H$0H H
HO H HO H
CH20H CH20H
L-glucose L-fructose

3. First determine whether the structure represents R-glyceraldehyde or S-glyceraldehyde. Then, because R-glyc-
eraldehyde = D-glyceraldehyde and S-glyceraldehyde = L-glyceraldehyde, you can answer the question.
H 0
" c,f'

l
H CH20H
a. HOCH2+0H b. HO+CH20H c. HO+H

~
H /c~ /c~
H ~O H ~O
L-glyceraldehyde L-glyceraldehyde D-glyceraldehyde

4. a. enantiomers because they are mirror images

b. diastereomers because the configuration of one asymmetric center is the same in both and the configu-
ration of the other asymmetric center is the opposite in both

5. a. n-ribose b. L-talose c. L-allose d. L-ribose

6. a. n-glucose = (2R,3S,4R,5R)-2,3,4,5,6-pentahydroxyhexanal
b. Because D-mannose is the C-2 epimer of D-glucose, the systematic name of D-mannose can be obtained
just by changing the configuration of the C-2 carbon in the systematic name of n-glucose.

D-mannose = ( 2S,3S,4R,5R )-2,3 ,4,5 ,6-pentahydroxyhexanal

c. D-Galactose is the C-4 epimer of n-glucose. Therefore, each of its carbon atoms, except C-4, has the
same configuration as it has in n-glucose.

D-galactose = ( 2R,3S,4S,5R )-2,3 ,4,5 ,6-pentahydroxyhexanal

d. L-Glucose is the mirror image of D-glucose, so each carbon in L-glucose has the opposite configuration
to that in n-glucose.
~

L-glucose = (2S,3R,4S,5S)-2,3,4,5,6-pentahydroxyhexanal

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 Chapter 20 685

7. o-psicose

8. a. A ketoheptose has four asymmetric centers ( 24 = 16 stereoisomers).

b. An aldoheptose has five asymmetric centers (25 = 32 stereoisomers).
c. A ketotriose does not have an asymmetric center; therefore, it has no stereoisomers.

9. CH20H
I/\
c=o
HO*H~:
H OH H20

H OH
CH20H
D-fructose an enolate ion an enediol

1l

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686 Chapter 20

10. Removal of an a-hydrogen creates an enol that can enolize back to the ketone (using the OH at C-2) or can
enolize to an aldehyde (using the OH at C-1). The aldehyde has a new asymmetric center (indicated by an*);
one of the epimers is D-glucose, and the other is D-mannose.

&;\H~:-
H0$c-rc.z. HO
CHOH
II
C-Q:
H
.C\ (\ H_LO

~
HO$H
CH-d_LH
II
C-OH
.0~.
.. :OH
..

H OH H20 H OH H OH
H OH H OH H OH

CH20H CH20H CH20H

D-fructose

1l
H"- ,.f'O (\_
c CH-O:
I r-11 ..
HO- *CHOH Hc0-H C-OH

H~±:H HO
H
H
OH

H+OH H OH
CH20H CH20H
D-glucose
D-mannose

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 Chapter 20 687

11. D-talose and D-galactose in addition to D-tagatose and D-sorbose.

CH20H CH-OH CH20H

I II I
c=o C-OH C-OH
II
HO
HO
H
H
~
H;o
HO$H
HO · H +
HO+H
C-OH

H OH H OH H OH
CH20H CH20H CH20H
D-tagatose

Hz01l HO- Hz01l HO-

H 0 H 0
"~
c "~
c CH20H CH20H
I I
HO H H OH C=O C=O
HO
HO
H
H +
HO
HO
H
H
HO$H
HO H + HO
H OH
H
H OH H OH H OH H OH
CH20H CH20H CH20H CH20H
D-talose D-galactose D-tagatose D-sorbose

12. a. When D-idose is reduced, D-iditol is formed.

H">c~o
CH20H
HO H HO H
H OH H OH
HO H HO H
H OH H OH
CH20H CH20H
D-idose D-iditol

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688 Chapter 20

b. When D-sorbose is reduced, C-2 becomes an asymmetric center, so both D-iditol and the C-2 epimer of
D-iditol (o-gulitol) are formed.

CH20H CH20H CH20H

I
c=o HO H H OH

HO
H$0H H
1. NaBH4
2. H 30+
HO
H OH
H
+
H
HO
OH
H
H OH H OH H OH
CH20H CH20H CH20H
o-sorbose D-iditol o-gulitol

13. a. 1. D-Altrose is reduced to the same alditol that D-talose is reduced to. The easiest way to answer this
question is to draw D-talose and its alditol. Then draw the monosaccharide with the same configu-
ration at C-2, C-3, C-4, and C-5 as D-talose, reversing the functional groups at C-1 and C-6. (Put
the primary alcohol group at the top and the aldehyde group at the bottom.) When this structure is
rotated 180° i~ the plane of the paper, the monosaccharide can be identified.

H 0 H 0
" c,f' CH20H CH20H " c ,f'

HO H HO H HO H HO H
HO H 1. NaBH4 HO H 1. NaBH4 HO H 180°,..
________
...,rotate H OH
2. H 3o+ 2. H 3o+
HO H HO H HO H H OH
H OH H OH H OH H OH
CH20H CH20H oc"- CH20H
o-talose the alditol of o-talose
O~ H
o-altrose

2. L-Gulose is reduced to the same alditol that D-glucose is reduced to.

H 0 H"- ,f'O
" c,f' CH 20H CH 20H c
H OH H OH H OH HO H
HO H HO H HO H rotate 180° HO H
1. NaBH4 1. NaBH4 ...,. ______ .,....
H OH 2. H3o+ H OH 2. H30+ H OH H OH
H OH H OH H OH HO H
CH 20H CH 20H CH20H
oc"-
o-glucose the alditol of
O~ H
L-gulose
o-glucose

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 Chapter 20 689
3. L-Galactose is reduced to the same alditol that n-galactose is reduced to.

H"'- ,.f'O H 0
c CH20H CH20H " c--?'
H OH H OH H OH HO H
HO H 1.NaBH4 HO H NaBH4
1. HO H ....rotate 180°,...
________ H OH
HO H 2.Hp+ HO H 2. H3o+ HO H H OH
H OH H OH H OH HO H
CH20H CH20H CH20H
#c"'-
D-galactose the alditol of D-galactose O~ H L-galactose

b. 1. The ketohexose (D-tagatose) with the same configuration at C-3, C-4, and C-5 as D-talose forms
the same alditol (n-talitol) that D-talose forms. The other alditol (n-galactitol) that is formed has
the opposite configuration at C-2.

CH20H CH20H CH20H

I
C=O HO H H OH

HO$H
HO H
1. NaBH4
2.H3o+
HO
HO
H
H
+
HO
HO
H
H
H OH H OH H OH
CH20H CH20H CH20H
D-tagatose D-talitol D-galactitol

2. Similarly, the ketohexose (n-psicose) with the same configuration at C-3, C-4, and C-5 as n-allose
forms the same alditol that p-allose forms. The other alditol (D-altritol) that is formed has the
opposite configuration at C-2.

CH20H CH20H CH20H

I
C=O H OH HO H

H$0H
H OH
1. NaBH4
2. H30+
H
H
OH
OH
+
H
H
OH
OH
H OH H OH H OH
CH20H CH20H CH20H
D-psicose D-allitol D-altritol

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690 Chapter 20

14. a. L-gulose (Note the similarity of this problem to Problem 13. a. 2.)

H 0 HO"'- ,f'O H"'- ,f'O

" c,f' c CH 20H c
H OH H OH H OH HO H
H
HO
H
H
OH -
HN0 3
11
HO
H
H
OH - HN0 3
11
HO
H OH
OH
..,.rotate ,.._ HO
180°
______
H
H
OH
H OH H OH H HO H
CH20H CH 20H
-f'c"'- -f'c"'-
0 OH 0 H
D-glucose L-gulose
D-glucaric acid

b. L-Gularic acid because it is also the oxidation product of L-gulose.

c. D-allose and L-allose, D-altrose and D-talose, L-altrose and L-talose, n-galactose and L-galactose

15. The monosaccharides,.are the aldoses with one additional carbon that are C-2 epimers and whose other
asymmetric centers have the same configuration as the given aldose.
a. D-gulose and D-idose b. L-xylose and L-lyxose

16. The monosaccharides are the aldoses whose C-1 carbon has been removed, whose C-2 carbon has been con-
verted to an aldehyde, and whose other asymmetric centers have the same configuration as the given aldose.
a. D-allose and D-altrose b. D-glucose and D-mannose c. L-allose and L-altrose

17. Solved in the text.

18. H .o H"'- ,f'O

" c,f' c
H"'- ,f'O
H OH HO H c H"'- ,f'O
HO H HO H
H~±:H c

=+~=
H OH H OH
H OH H OH H+OH
CH20H CH20H CH20H CH20H
D-glucose D-mannose D-arabinose D-erythrose
A B c D

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 Chapter 20 691

19. The hemiacetals in a and b have one asymmetric center; therefore, each has two stereoisomers. The hemi-
acetals in c and b have two asymmetric centers; therefore, each has four stereoisomers.

a. Solved in the text.

UH H'tJ H,DlH H,D

H3C OH
0
b.

c.
er d H OH

CH3CH2t: JH
c
CH3CH2CH2 OH

~H
d.

CH3CH2CH2
WH CH3CH2CH2

20. a. CH20H

H~H OH

OH

b.
eH 0H 0
2

HO OH

~
~20H
c.

H 0
HO OH HO OH
OH OH
a-o-glucose a-L-glucose
the mirror image of a-o-glucose

21.

HOi;
OH
OH

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692 Chapter 20,

22. H". ,.f'O

c
~H
=+~= ~H
CH20H
D-erythrose
OHOH
a-D-erythrofuranose
OHOH
,8-D-erythrofuranose

23. First recall that in the chair conformation, an a-anomer has the anomeric OH group in the axial position
and a /3-anomer has the anomeric OH group in the equatorial position. Then recall that glucose has all of
its OH groups in equatorial positions. Now this question can be answered easily.
All the OH groups in f3-n-glucose are in equatorial positions. Because /3-D-mannose is a C-2 epimer of
/3-D-glucose, the C-2 OH group of /3-D-mannose is the only one in the axial position.

24. a. D-Idose differs in configuration from D-glucose at C-2, C-3, and C-4. Therefore, the OH groups at C-2,
C-3, and C-4 in /3-n-idose are in axial positions.
b. n-Allose is a C-3 epimer of n-glucose. Therefore, the OH group at C-3 is in the axial position and
because it is the a-anomer, the OH group at C-1 (the anomeric carbon) is also in the axial position.

25.

H:~O\
HO CH20H HO CH 20H

HO~~O\
~
OH ~
~
0' OCH,cH, + H
~
HO

H H OCH2CH 3
,8-D-galactose ethyl ,8-D-galactoside ethyl a-D-galactoside

26. If more than a trace amount of acid is used; the amine that acts as a nucleophile when it forms the
N-glycoside becomes protonated, and a protonated amine is not a nucleophile.

27. Solved in the text.

28. a. a-n-talose (or a-D-talopyranose) (reducing; it is a hemiacetal)

b. methyl a-n-galactoside (or methyl a-n-galactopyranoside) (nonreducing; it is an acetal)
c. ethyl /3-D-psicoside (or ethyl /3-D-psicofuranoside) (nonreducing; it is an acetal)

29. specific rotation of glucose + specific rotation of fructose = -22.0

+52.7 + specific rotation of fructose = -22.0
specific rotation of fructose = -22.0 + (-52.7)
specific rotation of fructose = -74.7

30. a. Both sugars in the disaccharide are glucose.

b. It is a 1,6' -glycosidic linkage.

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 Chapter 20 693

31. a. Amylase has a-1,4 '-glycosidic linkages, whereas cellulose has {3-1,4 '-glycosidic linkages.
b. Amy lose has a-1,4 '-glycosidic linkages, whereas amylopectin has both a-1,4 '-glycosidic linkages
and a-1,6 '-glycosidic linkages.
c. Glycogen and amylopectin have the same kind of linkages, but glycogen has a higher frequency of
a-1,6 '-glycosidic linkages.
d. Cellulose has a hydroxy group at C-2, whereas chitin has an N-acetyl amino group at that position.

32. A proton is more easily lost from the C-3 OH group because the electrons that are left behind when the
proton is removed are delocalized onto an oxygen. When a proton is removed from the C-2 OH group, the
electrons that are left behind are delocalized onto a carbon. Because oxygen is more electronegative than
carbon, a negatively charged oxygen is more stable than a negatively charged carbon. Recall that the more
stable the base, the stronger its conjugate acid.

H H
g:

C-3

H H
0

HO C-2

33. a. People with type 0 blood can receive blood only from other people with type 0 blood because types
A, B, andAB blood have sugar components that type 0 bl~od does not have.
b. People with type AB blood can give blood only to other people with type AB blood because type AB
blood has sugar components that types A, B, and 0 blood do not have.

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694 Chapter 20

34. a. COOH b. coo- c. CH20H d. CH30

H OH H OH H OH
HO H HO H HO H
HO H HO H HO H OCH3
H OH H OH H OH
COOH CH20H CH20H

e. coo- f. OH OH

H OH
+
HO H
OCH2CH3
HO H
OCH2CH3
H OH
CH20H

g. HC=O

HO$H
HO H
H OH
CH20H

35. L-glucose L-allose

L-idose L-altrose
L-talose L-mannose

36. a. D-arabinose b. D-altrose c. D-Ribose

37. H". ,.f'O H". ,.f'O

H". ,.f'O
c c COOH COOH
c Kiliani-Fischer
H:±~H :~±: =~±:
H~+:H
synthesis H*OH
+ HO H +
H+OH H+OH H OH H=t=OH
CH20H CH20H CH20H COOH COOH
D-threose sugar A sugar B optically inactive optically active
D-xylose D-lyxose

38. a. No
b. No
c. D-altrose, D-glucose, D-mannose, D-gulose, D-idose, D-talose

39. a. 2S,3R,4R b. 2S,3S,4R c. 2R,3R,4R,5R d. 2S,3R,4R,5R e. 2S,3S,4R,5R

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 Chapter 20 695

40.

13-ethoxy-D-xylose a-ethoxy-D-xylose

OH OH

~O~o H~O
OH OH 0
1 OH

o-ethoxy-D-xylose y-ethoxy-D-xylose

41. a. alpha-ribose b. beta-glucose c. alpha-galactose

42. A monosaccharide with a molecular weight of 150 must have five carbons (5 Cs = 60, 5 Os = 80, and
10 Hs = 10 for a total of 150). A singlet at 9.5ppm for the proton NMR suggests that there must be an
aldehyde hydrogen. The following is a possible identity of the monosaccharide.
0 H

H OH
H OH
H OH
OH

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696 Chapter 20

43.
.0H-\)OH
H"- ~O H
"c /
O:
..
··-
HO: c
.. \ II
LH OH C-OH
HO
H
H
OH
H~±:H ~
H OH H+OH
CH20H CH 20H
D-glucose

H OH 1l
"'- / HQ:\ HOl}__H
C fl H7CIHOH CH20H CH20H
II _cH-OH '- In._ I
HO$Cir::~:
c-o:
H$c i~ ~ H$c~H
H OH H OH H+OH
11
C-OH
..

H OH
H OH H OH H+OH H OH

CH 20H CH20H CH20H CH 20H

HO-
H"-
c
J'O
~
H OH
OH H OH
~

OH H OH
OH H OH

CH 20H CH 20H
D-allose

44. H"- J'O

c H"- J'O
H$0H H+OH
H OH
c

H OH H OH
CH20H CH20H
D-ribose D-erythrose
A B

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 Chapter 20 697

HO HO~OH~H
45.
~q ]---VCH20H
HO~O
OH

46. The hexose is o-altrose.

1. Knowing that ( + )-glyceraldehyde is o-glyceraldehyde gives the configuration at C-5.
2. Knowing that the second Wohl degradation gives o-erythrose gives the configuration at C-4.
3. Knowing that the first Wohl degradation followed by oxidation gives an optically inactive aldaric acid
gives the configuration at C-3.
4. Knowing that the original hexose forms an optically active aldaric acid gives the configuration at C-2.

H'\... ~O
c
HO H
H OH H OH
H OH H OH H OH
H OH H OH H OH H OH
CH20H CH20H CH20H CH20H
o-altrose

47. CH20H CH20H+

HO~-
Ho
.C/) +OH==
H HO~OJ
HO .
HO H \)' HO ~H
+Cl- ··
+H20:

HO~C.H
20~Q·
HO H
HO
OH

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698 Chapter 20

48. There are two possible structures for an optically active five-carbon alditol formed from a Wohl degrada-
tion of a D-hexose:

HO$CH2~H HO$CH2~H
H OH *HO H
H OH H. OH
CH20H CH20H

All OH groups are in equatorial positions. Only the starred OH group is in an axial position.

The unknown aldohexose has only one OH group in an axial position. Therefore, the aldohexose that gives
the alditol on the left needs to have the OH on C-2 pointing to the left (so it will be axial). The other aldo-
hexose has an axial hydrogen, so it needs to have the OH on C-2 pointing to the right (so it will not be axial).
The two possible aldoses are D-mannose and D-galactose:

H 0 H"' ,f'O
"'c,f' c
HO H H OH
HO H HO H
H OH *HO H I
H OH H OH ~
CH20H CH20H
D-mannose D-galactose

If the two aldoses are reduced to alditols, the alditol of D-mannose will be optically active and the alditol of
l
D-galactose will be optically inactive. -

CH20H CH20H
HO H H OH
HO H HO H
H OH *HO H
H OH H OH
CH20H CH20H
alditol of D-mannose alditol of D-galactose

49. The hydrogen that is bonded to the anomeric carbon is the hydrogen that has its signal at the highest fre-
quency, because it is the only hydrogen that is bonded to a carbon that is bonded to two oxygens. So the
two anomeric hydrogen (one from the a-anomer and one from the f3-anomer) are responsible for the two
high-frequency doublets.

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 Chapter 20 699

50. COOH

HO
~-0 H

OH
the /3-n-glucuronide the a-n-glucuronide

51.
HO"'- ~O H 0 H 0 H 0
c "'~
c "'~
c "'~
c
H$0H
H OH
HN03 H$0H
H · OH
Kiliani-Fischer
H
H
OH
OH +
HO
H
H
OH
H OH H OH H OH H OH
c CH20H H OH H OH
0~ "'OH CH20H CH20H
optically inactive A c B

!Wohl
degradation !HN~ !HNO,

HO"'- ~O H 0 HO"'- ~O HO 0
c "'~
c c "'~
c
H+OH
=+~=
H OH HO H
H OH H OH + H OH

c CH20H H OH H OH
0 ~"'OH H OH H OH
optically inactive D
-1c -1c
o~ "oH o~ "oH
optically inactive optically active

52. 1. As Fischer did, we can narrow our search to eight aldohexoses because there are eight pairs of enantio-
mers. First, we need to find an aldopentose that forms ( + )-galactose as a product of a Kiliani-Fischer
synthesis. That sugar is the one known as (- )-lyxose. The Kiliani-Fischer synthesis on (- )-lyxose
yields two sugars with melting points that show them to be the sugars known as ( + )-galactose and
( + )-talose. Now we know that ( + )-galacto:Se and ( + )-talose are C-2 epimers. The eight aldohexoses
are sugars 1 and 2, 3 and 4, 5 and 6, or 7 and 8. (See page 990 of the text.)
2. When ( + )-galactose and ( + )-talose react with HN03, ( + )-galactose forms an optically inactive
aldaric acid and ( + )-talose forms an optically active aldaric acid. Therefore, ( + )-galactose and
( + )-talose are sugars 1 and 2 or 7 and 8. Because ( + )-galactose is the one that forms the optically
inactive aldaric acid, it is either sugar 1 or 7.

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700 Chapter 20

3. To determine the structure of ( + )-galactose, we can go back to (- )-lyxose, the sugar that forms sug-
ars 7 and 8 by a Kiliani-Fischer synthesis, and oxidize it with HN0 3 . Finding that the aldaric acid is
optically active allows us to conclude that ( + )-galactose is sugar 7, because the aldopentose that leads
to sugars 1 and 2 would give an optically inactive aldaric acid.

H'\,. ,f'O
c
H OH HO H
HO H HO H
HO H HO H
H OH H OH
CH20H CH20H
7 8
D-galactose D-talose

53. n-allose and n-idose. The only D-aldohexose that are oxidized to optically inactive aldaric acid after the
Wohl degradation are n':.allose and D-idose, as there are symmetry planes that exist within the molecules.

54.
HO~HOH n (\H-Cl
HO QH
0
H

lactose

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 Chapter 20 701

HO~o, HO~o, HO~°' HO~o,

55.

~o~O~O~O~
OH NH OH NH
/ /
O=C O=C
""-cH3 ""-cH3
hyaluronic acid

56. She can take a sample of one of the sugars and oxidize it with nitric acid to an aldaric acid or reduce it with
sodium borohydride to an alditol. If the product is optically active, the sugar was D-lyxose; if the product is
not optically active, the sugar was D-xylose.

H 0 H"'-. ,f'O
" c,f' COOR c COOR

HO$H
HO H
HN03
~
HO
HO
H
H
H$0H
HO H
HN03
~
H
HO
OH
H
H OH. H OH H OH H OH
CH20H COOR CH20H COOR
D-lyxose optically active o-xylose optically inactive

H"'-. ,f'O H 0

~ c " c,f'

I HO$H
HO
H
H
OH
1. NaB~

2.H3o+
:~±:H
H+OH
H$0H
HO
H
H
OH
1. NaBH4
2. H3o+
H*~:
HO
H
H
OH
CH20H CH20H CH20H CH20H
D-lyxose optically active D-xylose optically inactive

57. +
(H\_}
~N(\
H
/J H NH H NH2
H"'-.
C~
I
H-Cl "
?~.
,,jJ+ "cI /
'-...OH
R R H20: R

1l
(\ Hf:B
H 0 H 0/ \} H
+
/.NH 3
" c ,f' " c ,f' ""-c /v
I I R
/ (>--••
:OH
R R

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702 Chapter 20

58. HO
H OH
H
H OH

aldonic acid of D-allose

59. HO <o

c:
R HO
HO

.........____
H
H
H
H

HO 0

aldaric acid of D-allose

+
: rotate 180°
I

HO

H
H OH
S .........____
H OH

HO 0

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 Chapter 20 703

60.

HO~~o,
2 0~<:{)
HO~CH
HO CH20H
H0([0 ~o,
r jtto~OH IHo~OH
H\:P HO H HO
,8-maltose +er

2 0H0
HO~CH
CH 20H+ CH 20H .
HO~q;-) HO~O,
HO HO~+ HO~OH
HO + HO \ HO
c_OH H2 o:J
I
.. H
H 20:...._)

The /3-anomer will also be formed when H20 adds to the top of the plane of the oxocarbenium ion.

61. 10 aldaric acids

Each of the following pairs forms the same aldaric acid:

D-allose and L-allose L-altrose and L-talose

D-galactose and L-galactose D-gulose and L-glucose
n-altrose and D-talose L-gulose and n-glucose
Therefore, 12 aldohexoses form 6 aldaric acids. The other 4 aldohexoses each form a distinctive aldaric acid,
and 6 + 4 = 10.

62. We know the hexose is a ketohexose because it does not react with Br2 ; we know it is a 2-ketohexose
because if it were a 3-ketohexose, it would not be able to form a hemiacetal (because the hemiacetal would
have an unstable four-membered ring), and, therefore, would not undergo mutarotation.

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704 Chapter 20

Knowing that the hexose is oxidized by Tollens reagent to the aldonic acids D-talonic acid and D-galactonic
acid tells us that the aldonic acids and the ketohexose have the same configuration at C-3, C-4, and C-5.
Therefore, the hexose is D-tagatose.

COOH COOH CH20H

I
HO H H OH C=O
HO H HO H
HO$H
HO H HO H HO H
H OH H OH H OH
CH20H CH20H CH20H
D-talonic acid D-galactonic acid D-tagatose

63.
H
~·-
DO: D-OD H
r--:._ DO:
(~HOH .. ~CHOH
II n._
GDOH ..

~ <6 HO$ciE:
~~
HO$H
H OH
H OH H~±~H
H OH
H OH H+OH
CH20H I
CH20H CH20H
D-fructose with one deuterium

D-OD
1l '
~
CD20H
I ~CDOH
c=o ll_o.-
HO$H
H OH HO*c·
H OH
~:
H OH
H OH
CH20H
CH20H
D-fructose with two deuteriums

64. a. c. OH e.
Ho~J-O\·
HO~CH20H

OH

f.
~H~
d. HOCH2 O OH OH
/01-----r:-oH
HOCH2~-----.t.---uH
qH,OH
OHOH OH
HO OH

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 Chapter 20 705

65. Let A = the fraction of n-glucose in the a-form and B = the fraction of n-glucose in the /3-form.
A+B=l
B=l-A
specific rotation of A = 112.2
specific rotation of B = 18.7
specific rotation of the equilibrium mixture = 52.7
specific rotation of the mixture = specific rotation of A X fraction of n-glucose in the a-form +
specific rotation of B X fraction of n-glucose in the /3-form
52.7 = 112.2A + (1 - A) 18.7
52.7 = 112.2 A + 18.7 - 18.7 A
34.0 = 93.5A
A= 0.36
B = 0.64

This calculation shows that 36% is in the a-form and 64% is in the /3-form. This agrees with the values
given in Section 20.10.

66. Let A = the fraction of D-mannose in the a-form and B = the fraction of n-mannose in the /3-form.

A+B=l
B = -1 - A

specific rotation of A = 130.1

specific rotation of B = 51.4
specific rotation of the equilibrium mixture = 80.2
specific rotation of the mixture = specific rotation of A X fraction of mannose in the a-form +
specific rotation of B X fraction of mannose in the /3-form
80.2 = 130.1 A + 51.4 (1 - A)
80.2 =· 130.1 A + 51.4 - 5l.4A
28.8 = 78.7 A
A= 0.366
Therefore, 36.6% is a-n-mannose and 63.4% is ,B-n-mannose.

67. N
Ill
(c
lo~·-
H-c-o-H HO:
I ..
R

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706 Chapter 20

68. Silver oxide increases the leaving tendency of the iodide ion from methyl iodide, thereby allowing the
nucleophilic substitution reaction to take place with the poorly nucleophilic alcohol groups. Because man-
nose is missing the methyl substituent on the oxygen at C-6, the disaccharide must be formed using the C-6
OH group of mannose and the anomeric carbon of galactose.

HO CH 2 0H

~o,o-----cHz
HO~~O
OH HO -O
D-galactose HO
D-mannose OH

69. D-mannose will most likely exist as a pyranose because:

(1) the pyranose is particularly stable since all the large substituents are trans to each other, minimum
torsional strains and
(2) the furanose has two of its OH groups in the unstable cis position relative to each other.

H
HO~·''
0
HO OHOH
OH
H
H H
D-mannofuranose D-mannopyranose

70. From its molecular formula and the fact that only glucose is formed when trehalose is hydrolyzed, we
know that it is a disaccharide. Trehalose can be a nonreducing sugar only if the anomeric carbon of one
glucose is connected to the anomeric carbon of the other glucose. Because it can be hydrolyzed by maltase,
its glycosidic linkage must have the same geometry as an a-1,4 '-glycosidic linkage. Therefore, the OH
group attached to the anomeric carbon of the glucose on the left must be axial, and the OH group attached
to the anomeric carbon of the glucose on the right must be equatorial. (Notice that the glucose on the right
is drawn upside down and is reversed horizontally.) I

HO~CH
2 0H0
HO HO
OHo~OH
b~OH
CH 2 0H

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 Chapter 20 707

71. HzO~ Hz~~

.( H
I
HC = N-hemoglobin
HzQ:
(
n
HC = NH-hemoglobm
. H
\ HC- NH-hemoglobin
H ( OH
~In.

~H
H OH
HO H ~-
HO H ~ HO$C
'-~
H OH H OH H OH
H OH H OH H OH
·-.
CH20H CH20H CH20H

1l
CH2NH-hemoglobin CH2NH-hemoglobin
I I Cl
C=O C=O-H HO·
HO ~ ~··
+ HO$H
H OH H OH
H OH H OH
CH20H CH20H
'·
72. Because all the glucose units have six-membered rings, the 5-position is never methylated.
2,3,4,6-tetra-O-methyl-n-glucose has only its I-position in an acetal linkage.
2,4,6-tri-0-methyl-n-glucose has its 1- and 3-positions in an acetal linkage.
2,3,4-tri-0-methyl-n-glucose has its 1- and 6-positions in an acetal linkage.
2,4-di-O-methyl-n-glucose has its 1-, 3-, and 6-positions in an acetal linkage.

CH20H These corners are not

r
methylene groups;
it is a convention used
0 O wh~n l'.nking Haworth
\ 3,6'-linkage
H~o-CH, ?_ _,,I~ /:roJ~"oo"

OH ~ CHz HO
1,6'-linkage
OH
~
0
OH

HO O-
OH HO O-CH2 1,6'-linkage
1,3'-linkage OH ~
OH
HO O-
OH

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708 Chapter 20

73. In the case of n-idose, the chair conformer with both the OH substituent at C-1 and the CH20H substituent
in axial positions (which is necessary for the formation of the anhydro form) has the OH substituents at
C-2, C-3, and C-4 in equatorial positions. Thus, this is a relatively stable conformer because three of the
five large substituents are in equatorial positions, where there is more room for a substituent.
In the case of D-glucose, the chair conformer with both the OH substituent at C-1 and the CH20H substituent
in axial positions has the OH substituents at C-2, C-3, and C-4 in axial positions. This is a relatively unstable
conformer because all the large substituents are in axial positions and will have unfavorable 1,3-diaxial
interactions.

/'

~
CH2--0

HQ~OH OH OH OH
anhydro form of D-idose anhydro form of D-glucose

Therefore, a large percentage of D-idose but only a small percentage of n-glucose exists in the anhydro
form at 100 °C.

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 Chapter 20 709

Chapter 20 Practice Test

1. Draw the product(s) of the following reactions:

a. H 0
" c,f'
H OH
HO H HN03
H OH Ll

H OH
CH20H
\

b. OH

HCI
OH

c. H 0
" c,f'

\
HO$H
HO H
l.HC=N
2. H2/Pd/BaS04
3. HCl,H20

\ H OH
CH20H

d. H"- ,f'O
\
c
H OH
H OH
H OH
CH20H

2. Indicate whether each of the following statements is true or false:

a. Glycogen contains a-1,4 ' - and {3-1,6 '-glycosidic linkages. T F
b. n-Mannose is a C-1 epimer of D-glucose. T F
c. n-Glucose and L-glucose are anomers. T F
d. n-Erythrose and D-threose are diastereomers. T F
d. Wohl degradations of n-glucose and n-gulose form the same aldopentose. T F

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710 Chapter 20

3. Which of the following sugars form an optically active aldaric acid?

H"- ,f'O
c
HO H H OH H OH H OH
HO H HO H H OH HO H
H OH H OH H OH HO H
H OH H OH H OH H OH
CH20H CH20H CH20H CH20H

I
4. When crystals of D-fructose are dissolved in a basic aqueous solution, two aldohexoses are obtained. Identify
the aldohexoses.

5. Draw three tetroses that form the same enol.

/
6. D-Talose and _ _ _ are reduced to the same alditol.

7. What is the main structural difference between amylose and cellulose?

8. What aldohexoses are formed from a Kiliani-Fischer synthesis starting with D-xylose?

9. What aldohexose is the C-3 epimer of D-glucose?

10. Draw the most stable chair conformer of /3-D-allose, a C-3 epimer of /3-D-glucose.

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