5.2: Classes of Monosaccharides and Handedness

 Learning Objectives

• Classify monosaccharides as aldoses or ketoses and as trioses, tetroses, pentoses, or hexoses.
• Observe and recognize the handedness of D- and L-saccharides.

The naturally occurring monosaccharides contain three to seven carbon atoms per molecule. Monosaccharides of specific sizes may be indicated by names composed of a stem denoting the number of carbon atoms and the suffix -ose. For example, the terms triose, tetrose, pentose, and hexose signify monosaccharides with, respectively, three, four, five, and six carbon atoms. Monosaccharides are also classified as aldoses or ketoses. Those monosaccharides that contain an aldehyde functional group are called aldoses; those containing a ketone functional group on the second carbon atom are ketoses. Combining these classification systems gives general names that indicate both the type of carbonyl group and the number of carbon atoms in a molecule. Thus, monosaccharides are described as aldotetroses, aldopentoses, ketopentoses, ketoheptoses, and so forth. Glucose and fructose are specific examples of an aldohexose and a ketohexose, respectively.

Example \(\PageIndex{1}\)

Draw an example of each type of compound.

1. a ketopentose
2. an aldotetrose

Solution

1. The structure must have five carbon atoms with the second carbon atom being a carbonyl group and the other four carbon atoms each having an OH group attached. Several structures are possible, but one example is shown.

   

• The structure must have four carbon atoms with the first carbon atom part of the aldehyde functional group. The other three carbon atoms each have an OH group attached. Several structures are possible, but one example is shown.

  

Exercise \(\PageIndex{1}\)

Draw an example of each type of compound.

1. an aldohexose
2. a ketotetrose

The simplest sugars are the trioses. The possible trioses are shown in part (a) of Figure \(\PageIndex{1}\); glyceraldehyde is an aldotriose, while dihydroxyacetone is a ketotriose. Notice that two structures are shown for glyceraldehyde. These structures are stereoisomers, and hence are isomers having the same structural formula but differing in the arrangement of atoms or groups of atoms in three-dimensional space. If you make models of the two stereoisomers of glyceraldehyde, you will find that you cannot place one model on top of the other and have each functional group point in the same direction. However, if you place one of the models in front of a mirror, the image in the mirror will be identical to the second stereoisomer in part (b) of Figure \(\PageIndex{1}\). Molecules that are nonsuperimposable (nonidentical) mirror images of each other are a type of stereoisomer called enantiomers (Greek enantios, meaning “opposite”). We can think of pairs of molecules that are mirror images of each other much the same way we can consider right and left hands, which are mirror images of each other. This will be discussed more fully below.

Figure \(\PageIndex{1}\): Structures of the Trioses. (a) D- and L-glyceraldehyde are mirror images of each other and represent a pair of enantiomers. (b) A ball-and-stick model of D-glyceraldehyde is reflected in a mirror. Note that the reflection has the same structure as L-glyceraldehyde.

A key characteristic of enantiomers is that they have a carbon atom to which four different groups are attached. Note, for example, the four different groups attached to the central carbon atom of glyceraldehyde (part (a) of Figure \(\PageIndex{1}\)). A carbon atom that has four different groups attached is a chiral carbon. If a molecule contains one or more chiral carbons, it is likely to exist as two or more stereoisomers. Dihydroxyacetone does not contain a chiral carbon and thus does not exist as a pair of stereoisomers. Glyceraldehyde, however, has a chiral carbon and exists as a pair of enantiomers. Except for the direction in which each enantiomer rotates plane-polarized light, these two molecules have identical physical properties. One enantiomer has a specific rotation of +8.7°, while the other has a specific rotation of −8.7°.

H. Emil Fischer, a German chemist, developed the convention commonly used for writing two-dimensional representations of the monosaccharides, such as those in part (a) of Figure \(\PageIndex{1}\). In these structural formulas, the aldehyde group is written at the top, and the hydrogen atoms and OH groups that are attached to each chiral carbon are written to the right or left. (If the monosaccharide is a ketose, the ketone functional group is the second carbon atom.) Vertical lines represent bonds pointing away from you, while horizontal lines represent bonds coming toward you. The formulas of chiral molecules represented in this manner are referred to as Fischer projections.

The two enantiomers of glyceraldehyde are especially important because monosaccharides with more than three carbon atoms can be considered as being derived from them. Thus, D- and L-glyceraldehyde provide reference points for designating and drawing all other monosaccharides. Sugars whose Fischer projections terminate in the same configuration as D-glyceraldehyde are designated as D sugars; those derived from L-glyceraldehyde are designated as L sugars.

By convention, the penultimate (next-to-last) carbon atom has been chosen as the carbon atom that determines if a sugar is D or L. It is the chiral carbon farthest from the aldehyde or ketone functional group.

More on Mirror Images and Handedness in Molecules

Understanding the causes and consequences of molecular handedness is crucial to understanding organic and biomolecules. 

Figure 5.1: Like the mountain whose image is reflected in a lake, many organic molecules also have mirror-image counterparts. (credit: modification of work “Crystal Lake sunrise reflection” by Sandy Horvath-Dori/Wikimedia Commons, CC BY 2.0)

Are you right-handed or left-handed? You may not spend much time thinking about it, but handedness plays a surprisingly large role in your daily activities. Many musical instruments, such as oboes and clarinets, have a handedness to them; the last available softball glove always fits the wrong hand. The reason for these difficulties is that our hands aren’t identical; rather, they’re mirror images. When you hold a left hand up to a mirror, the image you see looks like a right hand. Try it.

Handedness is also important in organic and biological chemistry, where it arises primarily as a consequence of carbon atoms that can bond to four different groups in a different mirror-image order. Many drugs and almost all the molecules in our bodies—amino acids, carbohydrates, nucleic acids, and many more—have a handedness. Furthermore, molecular handedness enables the precise interactions between enzymes and their substrates that are involved in the hundreds of thousands of chemical reactions on which life is based.

Summary

Monosaccharides can be classified by the number of carbon atoms in the structure and/or the type of carbonyl group they contain (aldose or ketose). Most monosaccharides contain at least one chiral carbon and can form stereoisomers. Enantiomers are a specific type of stereoisomers that are mirror images of each other.