7P1-1 Monosaccharides Monosaccharide stereoisomers Cyclic structures Reactions Examples and derivatives Di and oligosaccharides Polysaccharides Homo and heteropolysaccharides Glycoconjugates Chapter 7: Outline

7P1-2 Originally, carbohydrates were those compounds having the formula C n (H 2 O) n. Only monosaccharides or simple sugars fit the formula. As more complex carbohydrates were discovered, the term came to mean compounds associated with polyhydroxy aldehydes and ketones.

7P Monosaccharides polyhydroxy Aldehydes are aldoses Ketones are ketoses 3=triose 4=tetrose 5=pentose 6=hexose Number of carbons

7P1-4 Monosaccharides: generic names The generic name for a simple sugar begins with the carbonyl prefix aldo or keto and ends with the term for the number of carbons. An aldose with three carbons is called an aldotriose. A ketose with three carbons is a ketotriose. What is the name for a six carbon aldehyde sugar? What is the name for a five carbon ketone sugar? aldohexose ketopentose

7P1-5 Dihydroxyacetone Is a ketotriose

7P1-6 Glyceraldehyde Is an aldotriose Glyceraldehyde exists in two stereoisomeric forms because the starred carbon is a stereocenter: it has four different groups attached.

7P1-7 The stereoisomers of glycer- aldehyde are designated D or L. The D isomer has the OH on the stereocenter to the right. The L isomer has the OH on the left. stereocenter

7P1-8 Glyceraldehyde: 3 The stereoisomeric forms of glycer- aldehyde are enantiomers: nonsuper- imposable mirror image molecules. Perspective drawings of the two enantiomers of glyceraldehyde are on the next slide. A stereo view is on slide 11. Remember, barred bonds ( ) recede behind the plane of the screen and wedge ( ) bonds project in front of the plane.

7P1-9 Perspective View

7P1-10 Carbonyl group CH 2 OH group OH group H atom View with blue lens on the left eye. Stereoscopic view of glyceraldehyde

7P1-11 Fischer Projections In a Fischer projection, the sugar molecule is oriented so that the most oxidized carbon is to the top. The stereocenter carbons are arranged so that the groups not part of the main chain project horizontally toward the viewer. The molecule is in the all eclipsed form.

7P1-12 Monosaccharides are drawn in Fischer projections with the most oxidized carbon closest to the top. The carbons are numbered from the top. If the the stereocenter with the highest number has the OH to the right, the sugar is D. If the OH is to the left, the sugar is L. Most common sugars are in the D form. Note: Fisher projections represent an all eclipsed conformation.

7P

7P1-14 These diastereomers are also epimers, they differ in configuration at only one stereo- center (colored dot).

7P1-15 Cyclic forms for sugars Most simple sugars of four or more carbons exist in the cyclic (hemiacetal or hemiketal) form. A hydroxy group in the sugar reacts with the carbonyl group. The new OH bearing carbon is now a stereo center and is called an anomeric carbon. If the OH on the ring is “up” the carbon is , if the OH is “down” it is .

7P1-16 Cyclic forms for sugars-2 Fischer projections for  D glucose

7P1-17 Cyclic forms for sugars-3 Haworth 1. Draw a five- or six-membered ring 2. Anomeric C to right of O. Place OH up or down. Left on Fischer, up on ring. 3. In D- sugars, the last C is always up.

7P1-18 Cyclic forms for sugars-4 Haworth Anomeric C  -OH

7P1-19 Cyclic forms for sugars-5 Glucose Pyranose ring form

7P1-20 Cyclic forms for sugars-6 The alpha and beta forms of cyclic sugars are said to be anomers. They differ in configuration about the hemiacetal or hemiketal carbon.

7P1-21 Cyclic forms for sugars-7 Ribose also exists mainly in the cyclic form.

7P1-22  D-glucose: the chair conformer Four of the five bulky groups (OH and CH 2 OH on C 2,3,4,5) on the ring are in the more stable equitorial positions!

7P1-23 Oxidation of Monosac charides Aldoses react with Tollen’s reagent (Ag(NH 3 ) 2 + ) to give a lactone (cyclic ester). The silver ion plates out as a mirror. Ag(NH 3 ) Ag(mirror) Cu 2+ + Cu 2 O (red-orange) Benedict’s reagent (a blue copper ion solution) also gives a lactone. The blue color fades as reaction occurs.

7P1-24 Aldehyde oxid’n  aldonic acid Oxidation of Monosaccharides-2 Term CH 2 OH oxid’n  uronic acid

7P1-25 Oxidation of Monosac charides-3 Aldehyde + term CH 2 OH oxid’n  aldaric acid

7P1-26 Reduction of Monosaccharides The most important reduced sugar is deoxyribose. (In DNA) When the carbonyl of a sugar is reduced to an alcohol, alditols are produced. The two shown above are used to sweeten nonsugar gum.

7P1-27 Isomerization Isomerization of mono- saccharides occurs through an enediol.

7P1-28 Esters of Monosaccharides The OH groups of sugars can react with phosphoric acid to give phosphate esters.

7P1-29 Glycosides The anomeric OH can react with another OH on an alcohol or sugar. Water is lost to form an acetal/ketal Acetal link: R-O-C-O-R Acetal carbon

7P1-30 Important Monosaccharides

7P1-31 Amino Sugars

7P1-32 Amino Sugars-2