26 C!#$%&’!()*...26.4 ISOMERIZATIONS OF MONOSACCHARIDES Epimers Figure 26.4 Isomerization of...

C!"#$%&'"!()*26

SUCROSE

26.3 CHIRALITY OF MONOSACCHARIDES

(R)-glyceraldehyde[!]D = + 13.5o

Fischer projection25

D-fructose

Fischer projection

D-galactose

Fischer projection

carbonyl group at top carbonyl near top

26.3 CHIRALITY OF MONOSACCHARIDESAldoses

(CH2OH)n

a D aldose

(CH2OH)n

an L aldose

mirror plane

D-ribose

D-fructose

D-glyceraldehyde D-glucose

D-allose

D-altrose

D-glucose

D-mannose

Aldohexoses

D-gulose

D-idose

D-galactose

D-talose

D-erythrose

CH2OHD-glyceraldehyde

Aldotriose

D-arabinose

D-lyxose

D-threose

OHHAldotetroses

D-ribose

D-xylose

Aldopentoses

Figure 26.1 Structures of D-Aldoses

Figure 26.2 Enantiomeric Relationship of D- and L-Monosaccharides!e D- and L-monosaccharides have reversed, mirror image configurations at every chiral center.

mirror

D-glucose

Determines D configuration

D-gluco configuration

D-glucose

Determines L configuration

L-gluco configuration

26.3 CHIRALITY OF MONOSACCHARIDESKetoses

D-erythulose

CH2OHdihydroxyacetone

Ketotriose

Ketotetrose

D-ribulose

D-xylulose

Ketopentoses

D-sorbose D-psicose D-fructose

D-tagatose

Ketohexoses

Figure 26.3 Structures of D-2-Ketoses

26.3 CHIRALITY OF MONOSACCHARIDESLess Common Monosaccharides

D-apiose

OHHOCH2

(a 3-ketopentose)

2-deoxy-D-ribose

D-2-glucosamine

N-acetyl-D-2-glucosamine

H C CH3

26.4 ISOMERIZATIONS OF MONOSACCHARIDESEpimers

D-galactose

D-glucose

D-mannose

C-4 epimers

C-2 epimers

Repimer 1 epimer 2

enediol(E and Z)

26.4 ISOMERIZATIONS OF MONOSACCHARIDESEpimers

Figure 26.4 Isomerization of Aldoses via an Enediol Intermediate

enediolD-glucose

D-mannose

not chiral

26.4 ISOMERIZATIONS OF MONOSACCHARIDESInterconversion of Aldoses and Ketoses

R(an aldolse) (a ketose)

(an enediol)

D-fructose-6-phosphate

CH2OPO32-

D-glucose-6-phosphate

CH2OPO32-

Hglucose-6-phosphateisomerase

26.5 CYCLIC MONOSACCHARIDES: HEMIACETALS AND HEMIKETALS

D-glucose !-D-glucopyranose

"-D-glucopyranose

furan pyran

5-hydroxypentanal

K = 20CO

C-1 CHO group

C-5 hydroxyl group

C-5 hydroxyl groupbond formation gives hemiacetal

rotation around C-3 C-4 ! bond

D-glucose

C-1 axial OH

!-D-glucopyranose "-D-glucopyranose

C-1 equatorial OH

!-D-fructofuranose

D-fructose

HO HOH

"-D-fructofuranose

Table 26.1Composition of Monosaccharides at Equilibrium in Solution (in percent)Monosaccharide Pyranose Furanose

! " ! "D-glucose 36 64D-mannose 67 32 0.8 0.2D-galactose 31 69D-allose 18 70 5 7D-altrose 27 40 20 13D-idose 38 38 10 14D-talose 40 29 20 11D-arabinose 63 34 2 1D-ribose 20 56 6 18D-xylose 27 63D-fructose 2 66 7 25

26.5 CYCLIC MONOSACCHARIDES: HEMIACETALS AND HEMIKETALSHaworth Projection Formulas

Figure 26.5 Haworth Projections of a Pyranose and a Furanose

Haworth projection of !-D-glucopyranose

OHOH2C

Haworth projection of "-D-fructofuranose

The C-6 CH2OH group is "up" in a Haworth projection of a D-pyranose or D-furanose.

The "-hydroxy group at C-1 is"down" in a Haworth projection of an "-D-pyranose or furanose. It is "up" in the ! anomer.

26.5 CYCLIC MONOSACCHARIDES: HEMIACETALS AND HEMIKETALSMutarotation

D-glucose!-D-glucopyranose

crystalize frommethanol

!-D-glucopyranosemp 146o

[!]D = + 112.2o

"-D-glucopyranose

crystalize fromacetic acid

"-D-glucopyranosemp 150o

[!]D = + 18.7o

26.6 REDUCTION AND OXIDATION OF MONOSACCHARIDESReduction of Monosaccharides

D-glucitol (D-sorbitol) (an alditol)

reduced

D-glucitol

26.6 REDUCTION AND OXIDATION OF MONOSACCHARIDESOxidation of Monosaccharides

D-gluconic acid(an aldonic acid)

oxidized

D-gluconic acid

D-glucaric acid(an aldaric acid)

oxidized

1o alcohol

D-glucaric acid

!-D-glucopyranose

NADP+-dependentdehydrogenase

1o alcohol

D-glucuronic acid

26.7 GLYCOSIDES

C OR'R

H(a hemiacetal)

+ R'OHH+

C OR'R

(an acetal)

C OR'R

H(a hemiketal)

+ R'OHH+

C OR'R

(a ketal)

methyl !-D-glucopyranoside

!-glycosidic bond

aglycone

26.7 GLYCOSIDES

resonance-stabilized oxocarbocation intermediate

!-D-glucose

26.7 GLYCOSIDESFigure 26.7 Formation of ! and " Glysosides

methyl !-D-glycopyranoside

Hmethyl "-D-glycopyranoside

26.8 DISACCHARIDESMaltose

OH!-(1,4') glycosidic bond

4-O-(!-D-glucopyranosyl)-"-D-glucopyranose (maltose)

"-anomer of glucose,the agylcone.

26.8 DISACCHARIDESMaltose

Figure 26.8 Molecular Model of Maltose.!e monosaccharide unit on the left is the hemiacetal of the !-D-glucopyranosyl unit. It is linked by an !-(1,4’) glycosidic bond to "-D-glucopyranose, the aglycone. !e oxygen atom of the glycosidic bond is approximately in the center of the structure, between the two rings. It is projected down, axial, and therefore !. It is linked to C-4 of the aglycone, and so the link is axial-equatorial.

4-O-(!-D-glucopyranosyl)-"-D-glucopyranose (maltose)

"-D-glucopyranose unit,the aglycone

"-equatorial hydroxyl group

!-D-glucopyranosylunit

!-axial oxygen of (1,4’)-gycosidic bond

26.8 DISACCHARIDESCellobiose

!-(1,4') glycosidic bond

4-O-(!-D-glucopyranosyl)-!-D-glucopyranose (cellobiose)

!-anomer of glucose,the agylcone.

!-D-glucopyranosyl unit

26.8 DISACCHARIDESCellobiose

Figure 26.9 Molecular Model of Cellobiose!e monosaccharide unit on the left is the !-D-glucopyranosyl portion of cellobiose. It is linked by a !-(1,4’) glycosidic bond to !-D-glucopyranose, the aglycone. !e oxygen atom of the glycosidic bond is approximately in the center of the structure, between the two rings. It is projected up, equa-torial, and therefore it is !. It is linked to C-4 of the aglycone, and so the link is equatorial-equatorial.

!-D-glucopyranoseunit, the aglycone

!-equatorial hydroxyl group

!-glycosidic bond

1 4’

26.8 DISACCHARIDESLactose

!-D-glucopyranosyl unit

4-O-(!-D-galactopyranosyl)-!-D-glucopyranose (lactose)

!-D-galactopyranosyl unit

C-4 epimer of glucose

Figure 26.10 Molecular Model of Lactose!e monosaccharide unit on the left is the !-D-galactopyranosyl portion of cellobiose. It is linked by a !-(1,4’) glycosidic bond to !-D-glucopyranose, the aglycone. Galactose is the C-4 epimer of glucose. !us, the hydroxyl group at C-4, which is equatorial in glucose, is axial in galactose.

4-O-(!-D-galactopyranosyl)-!-D-glucopyranose (lactose)

!-D-galactopyranosylunit

!-D-glucopyranoseunit, the aglycone

!-equatorial hydroxyl group

!-glycosidic bond

C-4 epimer of glucose, axialhydroxyl group

1 4’

26.8 DISACCHARIDESSucrose

!-anomer of glucose

!-D-glucopyranosyl-"-D-fructofuranoside (sucrose)

"-anomer of fructose

CH2OHH

(1,2')-glycosidic bond

Figure 26.11 Molecular Model of Sucrose!e monosaccharide unit on the left is the !-D-galactopyranosyl portion of sucrose. It is linked by a (1,2’) glycosidic bond to "-D-fructofuranose. !us, the anomeric carbons of the monomers are linked by a glycosidic bond. Sucrose is an acetal. !erefore, it is a nonreducing sugar.

26.8 DISACCHARIDESSucrose

!-D-glucopyranosyl-"-D-fructofuranoside (sucrose)

"-D-fructofuranoseunit

26.9 POLYSACCHARIDES

!-(1,4')-glycosidic bonds

cellulose

amylose

"-(1,4')-glycosidic bonds

amylopectin (or glycogen)

"-(1,4')-glycosidic bonds

"-(1,6')-glycosidic bonds at branch points

Figure 26.12 Structures of Polysaccharides

26.9 POLYSACCHARIDES

Trisaccharide segment of amylose

!-(1,4’)-glycosidic bonds4’

!-D-glucopyranosyl groups

4’ 4’

Figure 26.13 Three !-D-Glucopyranosyl Groups in AmyloseWhen we say that a polymer is “linear” we mean that the polymer contains no branches. Amylose coils into a helix.

26.10 CHEMICAL DETERMINATION OF MONOSACCHARIDE STRUCTURESPeriodate Oxidation

vicinal diol in monosaccharide

HIO4 C

aldehyde or ketone

vicinal diol at 1o alcohol

an aldehyde

formaldehyde

26.10 CHEMICAL DETERMINATION OF MONOSACCHARIDE STRUCTURESPeriodate Oxidation

(an aldose)

formic acid

(an aldehyde)+ H2O

(a ketose)

HIO4 CH2 Oformaldehyde

(a carboxylic acid)

OHH + O C O

26.10 CHEMICAL DETERMINATION OF MONOSACCHARIDE STRUCTURESOxidation and Optical Activity

D-galactose

optically inactive aldaric acid

plane of symmetry

26.10 CHEMICAL DETERMINATION OF MONOSACCHARIDE STRUCTURESFormation of Osazones

(CH2OH)n

(an aldose)

OHH NH2NHC6H5

(CH2OH)n

NHNHC6H5

(an osazone)

(CH2OH)n

(a ketose)

O NH2NHC6H5

(CH2OH)n

NHNHC6H5

(an osazone)

26.10 CHEMICAL DETERMINATION OF MONOSACCHARIDE STRUCTURESChain Extension of Aldoses

D-ribose

D-allose

D-altrose

oxidation

D-aldaric acid(optically inactive)

(+)-D-altraric acid

oxidation

26.10 CHEMICAL DETERMINATION OF MONOSACCHARIDE STRUCTURESChain Shortening of Aldoses

(one diastereomer)

(an oxime)

CH3O C

OHH+ CH3OH+CN

26.11 DETERMINATION OF RING SIZE

methyl !-D-ribofuranoside

OHOCH3

methyl !-D-ribopyranoside

methyl !-D-ribofuranoside

- OC C

H CHO CHO

dialdehyde product

OHOCH3

methyl !-D-ribopyranoside

dialdehyde product

+ HCO2HC H

C OCH3

!-D-glucopyranose

(CH3)2SO4O

methyl 2,3,4,6-tetra-O-methyl-!-D-glucopyranoside

2,3,4,6-tetra-O-methyl-!-D-glucopyranose

26.11 DETERMINATION OF RING SIZE

2,3,4,6-tetra-O-methyl-D-glucose

C OCH3

C HCH3O

CH2OCH3

oxidation

C OCH3

C HCH3O

dicarboxylic acid product

26.12 CHEMICAL DETERMINATION OF DISACCHARIDE STRUCTURE

OHOCH2

OHHOCH2

(CH3)2SO4

lactose

OCH3OCH2

CH3OCH2

octamethyllactose

OCH3OCH2

CH3OCH2

H3O+ OOH

CH2OCH3

2,3,4,6-tetra-O-methyl-D-galactose 2,3,6-tri-O-methyl-D-glucoseoctamethyllactose

26.13 HUMAN BLOOD GROUP ANTIGENS

N-acetylgalactosamine (GalNAc)

N-acetylglucosamine (GlcNAc)

6-deoxy-a-L-galactose (a-L-fucose)

!-GalNAcOH

!-GlcNAc

CH3OCH3

"-L-fucose

Type A

Oprotein

!-GlcNAc

"-L-fucose

Type B

Oprotein

!-GlcNAc

galactose

"-L-fucose

Type O

Oprotein

Type O Blood Group Antigen

!-D-galactopyranosyl

"-L-fucopyranosyl!-GlcNAc group

"-(1,2’)-glycosidic bond

!-(1,4’)-glycosidic bond

26 C!#$%&’!()*...26.4 ISOMERIZATIONS OF MONOSACCHARIDES Epimers Figure 26.4 Isomerization of...

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