11.1 Chapter 11 Educational Goals 1. Given a Fischer projection of a monosaccharide, classify it as either aldoses or ketoses. 2. Given a Fischer projection of a monosaccharide, classify it by the number of carbons it contains. 3. Given a Fischer projection of a monosaccharide, identify it as a D-sugar or L-sugar. 4, Given a Fischer projection of a monosaccharide, identify chiral carbons and determine the number of stereoisomers that ate possible. 5. Identify four common types of monosaccharide derivatives. 6. Predict the products when a monosaccharide reacts with a reducing agent or with Benedict's reagent. 7. Define the term anomer and explain the difference between a and B anomers. 8. Understand and describe mutarotation, 9. Given its Haworth projection, identify a monosaccharide either a pyranose or a furanose. 10. Identify the anomeric carbon in Haworth structures. 11. Compare and contrast monosaccharides, disaccharides, oligosaccharides, and polysaccharides. 12. Given the structure of an oligosaccharide or polysaccharide, identify the glycosidic bonds) and characterize the glycosidic linkage by the bonding pattern [for example: B(1—4)}. 13. Given the Haworth structures of two monosaccharides, be able to draw the disaccharide that is formed when they are connected by a glycosidic bond, 14, Understand the difference between homopolysaccharides and heteropolysaccharides. 15. Compare and contrast the two components of starch. 16. Compare and contrast amylopectin and glycogen. 17. \dentify acetal and hemiacetal bonding patterns in carbohydrates. TC 44011.2 Introduction to Monosaccharides Monosaccharides are the smallest carbohydrates and serve as the building blocks of larger carbohydrates. They are also referred to as simple sugars. Monosaccharides have the general chemical formula of Ca(H20)n; where n (the number of carbon atoms) can be three to seven. They are polyhydroxy! aldehydes or ketones: 1) Monosaccharides contain either an aldehyde group or a ketone bonding pattern. 2) Monosaccharides contain more than one hydroxy! OH) group, ‘Amonosaccharide that contains an aldehyde group is called an aldose. A monosaccharide that contains the ketone ‘bonding pattern is called a ketose. The general form of an aldose and a ketose are shown below: agree ketone bonding pattern u {au Il HO—C—-C Ij H (on x X=1toS X=0to4 general form of an aldose ‘general form of a ketose Note that the group in the blue-shaded region can repeat. For example, | have drawn (below) an aldose and a ketose structure where X = 3: HH OH OH HOH H OH H It otit It ott wil HO—c—c —c— HO —c—c¢ —c—c—C—C—H | It | It | | H OH OH OH H OH OH OH OH an aldose aketose HHH H HoH It HO CoC —C— CCC =H It 1 HOH OH OH HOH Click here to check answer 441Monosaccharides can be classified according to the number of carbons ‘they contain. These classifications are as shown in Table 11.1, pean Classification of Monosaccharides by the Number of Carbons they Contain [Number of Carbons| Classification Amonosaccharide may also be classified by both the number of carbons and whether it is an aldose or a ketose. This is done by using ‘the prefix “aldo” for aldoses, or “keto” for ketoses, in front of "triose,” uf td “tetrose,” "pentose," “hexose,” or “heptose.” For example, an aldose a ueeee that contains five carbons is an aldopentose. 5 pentose 6 hexose 7 heptose Click here to check answer ‘Stereochemistry of Monosaccharides Except forthe ketotriose, monosaccharides contain at least ane chiral carbon. You learned that a chiral carbon is a carbon that is surrounded by four different groups. Molecules with just one chiral carbon have a pair of geometric isomers called enantiomers. Enantiomers have the same atomic connections, but a different three-dimensional arrangement of atoms, and are nonsuperimposable miror images of each other. Ifa molecule has more than one chiral carbon, then it will have more than one pair of enantiomers. The number of stereoisomers that a molecule has can be ‘calculated from the number of chiral carbons. I a monosaccharide has n chiral carbons, then it will have 2° stereoisomers. For example, ita molecule has three chiral carbons, then it will have 2° = (2 x2 x 2) = 8 stereoisomers (four pairs of enantiomers). For more details on chiral carbons and enantiomers, review section 5 of chapter 9. Example: How many stereoisomers are possible for the monosaccharide shown below? HOH HOH OH co: H OH OH OH OF Solution: Identify the number of chiral carbons, and then calculate the number of stereoisomers. + There are four chiral carbons in this molecule. The chiral carbons are highlighted red in the structure below. HOW OH OW 9 Ho—c. oH | HOH OH OH OH + Recall that a carbon is chiral if it is surrounded by four different groups; you must consider whether each of the entire ‘groups bonded to the carbon are different from each other. In this example, the left-most carbon is not chiral because it is bonded to two hydrogen atoms. The right-most carbon is not chiral because itis only bonded to three groups. Since this monosaccharide structure has four chiral carbons, there are 2 = (2 x 2.x 2 x 2) = 16 possible stereoisomers (cight pairs of enantiomers). 442‘The monosaccharide in the previous example has a molecular formula of CéHi20s. We found that there are 16 different molecules (stereoisomers) that share this molecular formula and structural formula. Most of the physical properties of ‘these 16 stereoisomers are quite similar; however, the way they each behave in biological systems can be very different. Let's consider the three dimensional arrangement of the atoms in the smaliest monosaccharide, glyceraldehyde, Glyceraldehyde has only one chiral carbon. H ° o= H | HO-C. -H | HOH glyceraldehyde ‘The chiral carbon in the structural formula above is highlighted in red; itis bonded to four diferent groups. In the structure below, I have highlighted the four offferent groups that surround the chiral carbon. H HO | Il HO—C. C-H | HOH Since there is one chiral carbon in glyceraldehyde, then there are 2° = 21 = 2 stereoisomers (one pair of enantiomers/ nonsuperimposable mirror images). Wedge and dash models of the pair of glyceraldehyde enantiomers are shown below. i \ CH | Enantiomers > | “iy Q Yeo wf wail (OH) (OH) of glyceraldehyde enantiomers (nonsuperimposable mirror images) In order for professionals in healthcare, engineering, and science fields to discuss and depict the various monosaccharide stereoisomers, itis necessary to be able to draw two-dimensional (lat) structural formulas on a page or computer display, such that they still contain the three-dimensional information particular to each stereoisomer. In previous chapters, we used the wedge and dash system to retain the three. dimensional information on a flat surface. For monosaccharides, Fischer projections are used for this purpose. They were first described and used by Emil Fischer (1852 1919). Fischer was the 1902 recipient of the Nobel Prize in Chemistry for his work on carbohydrates and other organic molecules called purines. Emil Fischer 443Fischer Projections Fisher projections are related to an imaginary “shadow” that would be produced if a chiral carbon and its four bonded groups were placed in a particular orientation between a light source and a surface. Of course, this is an imaginary concept since it is impossible to get a real shadow from a molecule. The concept is ilustrated in Figure 11.1. ‘The chiral carbon in the stereoisomer shown in Figure 11.1 is labeled with the letter “C” and shaded red. In Fischer projections, chiral carbons are implied to be at the intersection of a vertical and horizontal ine, as shown in the Fischer projection drawn in the bottom of Figure 11.4 Fischer's choice of the particular orientation of the chiral carbon and its four groups was arbitrary, any orientation could have been used; however, for consistency, one specific orientation needed to be chosen. ‘The chosen orientation of a chiral carbon land the four groups that are bonded to it relative to the drawing surface/page in all Fischer Projections is as follows: 1) The bonds from the chiral carbon to the other carbon atoms point at a downward angle (see the bonds from the chiral carbon (C) to Wand ¥ in Figure 11.1), and their shadows form vertical lines on the drawing surace/ Fischer projection. Figure 11.1 An Illustration of the Fischer Projection Concept stereoisomer shadow Fischer projection fictitious light projector (represented by a flashlight) generates the imaginary "shadow" that would be produced when a chiral carbon and its four bonded groups are placed in a particular orientation in between the light projector and the surface. Fischer projections are based on these imagined shadows of the groups and bonds around each chiral carbon in ‘a monosaccharide. 2) The bonds from the chiral carbon to the nonearbon groups (which will be an H and an OH) point at a upward angle (see the bonds from the chiral carbon (C) to X and Z in Figuro 11.1), and their shadows form horizontal lines on the rawing surface/Fischer projection. 3) For aldoses, the aldehyde group is positioned at the end of the molecule that is closest to the top of the page (position W in Ficure 11.1). For ketoses, the carbonyl carbon is positioned as close as possible to the end molecule that is nearest the top of the page. COrienting the groups around chiral carbons in relation to the drawing surface, as describe above, results in a preservation of the three-dimensional information that distinguishes each monosaccharide. 444LLet’s consider the Fischer projections for both of the glyceraldehyde stereoisomers. Recall that glyceraldehyde has ‘one chiral carbon (shaded red below). Since the other two carbons in glyceraldehyde are not chiral, | can use shorthand notation to simplify the structure. The aldehyde group is represented by “CHO.” ‘The Fischer projections for the two enantiomers of glyceraldehyde are: CHO CHO Hu OH HO: H CH,OH CH,OH We do not need to draw the bonds around the top or bottom carbon atoms because they are not chiral. Note that we raw the hydroxyl groups that are on the left-hand side of Fischer projections as “HO.” 445,For monosaccharides with more than one chiral carbon, Fischer projections must be drawn (or interpreted) by considering the orientation around each of the chiral carbons. This is done one chiral carbon at atime. As an example, let's consider aldotetroses, which contain two chiral carbons: HOH HO I HO—C: CoH H OH OH an aldotetrose Since aldotetroses each have two chiral carbons, there are 22 = (2 x 2) = 4 stereoisomers (two pairs of enantiomers). | have drawn the Fischer projections for the four aldotetrose stereoisomers (below). ab ak a SS ee (mirror images) (mirror images) Remember that a chiral carbon is located wherever lines cross (intersect) in Fischer projections. Note that the hydrogen (H) and the hydroxyl group (OH) positions are reversed on chiral carbons for each particular enantiomer pal. This is the case for all monosaccharide enantiomer pairs. ‘The illustration below is meant to help you understand the three-dimensional implications of Fischer projections for monosaccharides with more than one chiral carbon. In ths illustration, | have drawn both the wedge and dash representation and the Fischer projection of one of the aldotetrose stereoisomers. g ‘ Z CHO ‘e H—}— 00 | non aw j on cH,OH OHO Wedge and Dash Representation Fischer Projection Click here to check answerD- and L- Des ns for Monosaccharides Carbohydrates are most often referred to by their common names, all of which use the “-ose" suffix. A common name is assigned to each pair of enantiomers. In order to differentiate the two individual monosaccharides of an enantiomer pai, ‘D-'or‘L~’ designations are used with the common name. The ‘L~' designation is used for the enantiomer in which the chiral carbon that is furthest from the top of the Fischer projection has its hydroxy! group on the left. To remember this, you can think “L- for LEFT.” The ‘D-' designation is used for the other enantiomer of the pair. For example, you learned that aldotetroses each have two chiral carbons, therefore there are 22 = 4 aldotetrose stereoisomers (two pairs of enantiomers). | have drawn and used D- and L- designations for the Fischer projections of the four aldotetrose stereoisomers (below) Deerythrose {an enantiomer pair) L-erythrose D-threose —_L-threose (an enantiomer pair) | drew red-dashed boxes around the chiral carbons that are furthest from the top of their Fischer projections. Its the position of the hydroxy! group on these carbons that is responsible for the D- vs. L- designations. Note that when determining the D- vs. L- designations, we are interested in the orientation of the hydroxy! group on the chiral carbon ‘that is furthest from the top of the Fischer projection; this will ways be the second to the last (bottom) carbon because the bottom carbon is never chiral. Monosaccharides are produced in living organisms by chemical reactions, some of which require enzymes that can only produce one particular enantiomer. For example, the stereoisomer of glucose that is made in photosynthesis is D- glucose. Fischer projections for both ofthe glucose enantiomers are shown below. | drew ted-dashed boxes around the chiral carbons and hydroxyl groups responsible for the D- and L- designations. xo x0 nor won won = wfeon won won = ciLoH GiioH D-sheoss __L-gheoae {fan enantiomer pair) ‘The glucose enantiomer pair (D-glucose and L-glucose) are two of the sixteen aldchexose stereoisomers. There are ‘seven more aldchexose enantiomer pairs that can be drawn by vatying the positions of the H and OH on each side of a Fischer projection (as you did for the aldopentoses in the previous review problem). These seven other enantiomer pairs are differentiated from glucose, and each other, by their common names | do not require my students to memorize the common names and structures for particular monosaccharides, however, you should check with your own instructor to see if you are required to do so. 4a7