Monosaccharides Haworth structures

Carbohydrates Chiral Molecules Fischer Projections of Monosaccharides Haworth Structures of Monosaccharides Chemical Properties of Monosaccharides Disaccharides Polysaccharides... 

A Haworth structure for a monosaccharide is translated readily into a structure showing the true shape of the molecule. 

The Haworth structure tells us that a substituent that is above the general plane of the monosaccharide ring must also appear above the general plane of the chair whether this is axial or equatorial will depend on the carbon atom being considered. For example, looking at each carbon of 0-D-glucopyranose in turn, we find... 

In drawing cyclic Haworth structures of monosaccharides, certain rules should be followed so that all our structures will be consistent. First we must draw the ring with its oxygen to the back ... 

Monosaccharides are sweet-tasting solids that are very soluble in water. Noncarbohydrate low-calorie sweeteners such as aspartame have been developed as sugar substitutes. Pentoses and hexoses form cyclic hemiacetals or hemiketals whose structures can be represented by Haworth structures. Two isomers referred to as anomers (the a and p forms) are produced in the cyclization reaction. All monosaccharides are oxidized by Benedict s reagent and are called reducing sugars. Monosaccharides can react with alcohols to produce acetals or ketals that are called glycosides. 

Haworth Structures of Monosaccharides LEARNING GOAL Draw and identify the Haworth structures for monosaccharides. 

Haworth structure The ring structure of a monosaccharide, ketose A monosaccharide that contains a ketone group, lactose A disaccharide consisting of glucose and galactose found in milk and mUk products. 

Monosaccharides commonly form internal hemiacetals or hemiketals, in which the aldehyde or ketone group joins with a hydroxyl group of the same molecule, creating a cyclic structure this can be represented as a Haworth perspective formula. The carbon atom originally found in the aldehyde or ketone group (the anomeric carbon) can assume either of two configurations, a and /3, which are interconvertible by mutarotation. In the linear form, which is in equilibrium with the cyclized forms, the anomeric carbon is easily oxidized. 

Haworth projection common way of representing the cyclic structure of monosaccharides using a three-dimensional perspective. 

A major drawback of cyclic Fischer projections is the unrealistic manner in which the structures are depicted. In 1929, Haworth designed a representation to address this deficiency. Haworth projections provide a simple way to represent cyclic monosaccharides with a three-dimensional perspective. The following process allows the conversion of a Fischer projection into a Haworth representation ... 

William Mills described a similar convention to depict the structures of monosaccharides. While the ring atoms of the Haworth projections are oriented perpendicular to the paper, Mills chose to depict the carbon skeleton in the plane of the paper (Fig. 1.5). Although Fischer, Haworth, and Mills projections are useful tools for depicting the structures of carbohydrates, the planar nature of these representations does not provide an accurate picture of the actual geometry of the molecules. In order to understand carbohydrate function and reactivity, recognition of each distinct conformation and the properties associated with it is required [15]. 

Using methods similar to Fischer s, the straight-chain form of any monosaccharide can be worked out. As we have seen, however, monosaccharides exist mostly as cyclic pyra-nose or furanose hemiacetals. These hemiacetals are in equilibrium with the open-chain forms, so sugars can react like hemiacetals or like ketones and aldehydes. How can we freeze this equilibrium and determine the optimum ring size for any given sugar Sir Walter Haworth (inventor of the Haworth projection) used some simple chemistry to determine the pyranose structure of glucose in 1926. 

The Haworth projection formulas are neater ways of writing the ring forms shown in the equilibria above and yet preserving the configuration shown at each chiral carbon. It is not difficult to translate the open-chain structure for a monosaccharide into the Haworth ring structure. 

The configurations of monosaccharides are described by several types of formulas. As an example, the following formulas are shown for a-D-glucopyranose structural, Haworth, modified Fischer, and Fischer. In Fischer formulas the -H or -OH groups are above or below the plane formed by the hemiacetal bonds and the carbon chain (-H bonds are shown shorter). 

CONFORMATIONAL STRUCTURES Although Haworth projection formulas are often used to represent carbohydrate structure, they are oversimplifications. Bond angle analysis and X-ray analysis demonstrate that conformational formulas are more accurate representations of monosaccharide structure (Figure 7.10). Conformational structures are more accurate because they illustrate the puckered nature of sugar rings. 

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