Monosaccharides ketoses

Most, if not all, of the stable forms of crystalline aldose and ketose monosaccharides exist in the pyranose structure. Each in solution, as with D-glucose, exists as an equilibrium mixture of open chain and of a- and / -anomers of the cyclic forms. The cyclic five- and six-membered structures formulated below are an illustrative selection of monosaccharides. 

A monosaccharide can be a polyhydroxy aldehyde such as D-glucose or a polyhydroxy ketone such as o-liructose. Polyhydroxy aldehydes are called aldoses ( aid is for aldehyde ose is the suffix for a sugar), whereas polyhydroxy ketones are called ketoses. Monosaccharides are also classified according to the number of carbons they contain Monosaccharides with three carbons are trioses, those with four carbons are tetroses, those with five carbons are pentoses, and those with six and seven carbons are hexoses and heptoses, respectively. A six-carbon polyhydroxy aldehyde such as o-glucose is an aldo-hexose, whereas a six-carbon polyhydroxy ketone such as o-fructose is a ketohexose. 

Monosaccharides that contain an aldehyde group are called aldoses, whereas those containing a ketone group are ketoses. Monosaccharides are also classified by the number of carbon atoms as trioses, tetroses, etc. objective 5 (Section 7.4), Exercise 7.22. Most natural monosaccharides belong to the d family. 

Monosaccharides are divided into two major groups depending on whether their acyclic forms possess an aldehyde or a keto group, that is, whether they are aldoses or ketoses. Monosaccharides can also be grouped by the size of the ring that they form, for example, furanoses or pyranoses. Both aldoses and ketoses may be designated as to size, for example, as aldopentoses or 2-hexuloses (El Khadem, 1988). Sug-... 

There are obviously many aldose monosaccharides and many ketose monosaccharides, but the discussion will focus only on the d diastereomers, as with the aldoses. The triose is l,3-dihydroxy-2-propanone (41 also called glycerone) and the tetrose is d-glycero-tetrulose (42). Two pentoses are named d-ribulose (43) and d-xylulose (44) and four hexoses are named d-psicose (45), d-fructose (46), d-sor-bose (47), and d-tagatose (48). All of these compounds are ketoses and are further classified according to the number of carbon atoms, as noted in Section 28.1. For example, 42 is a ketotetrose, 43 is a ketopentose, and 45 is a ketohexose. For 43-48, cyclization is possible to form a hemiketal. Just as aldehydes and alcohols react to form a hemiacetal, ketones and alcohols react to form a hemiketal (see Chapter 18, Section, 18.6). For 43, a five-membered ring (a furanose) is formed if the terminal CH2OH unit (in violet) reacts with the ketone carbonyl. The two anomers formed are 49 (a-d-ribulofuranose) and 50 (P-d-ribulofuranose). 

Carbohydrates may be divided into monosaccharides, disaccharides and polysaccharides. The monosaccharides under certain conditions react as polyhydroxy-aldehydes or polyhydroxy-ketones two important representatives are glucose CjHjjO (an aldose) and fructose (laevulose) CgHuO, (a ketose). Upon hydrolysis di- and polysaccharides 3deld ultimately monosaccharides. Common disaccharides are sucrose, lactose and maltose (all of molecular formula C,2H2. 0,), whilst starch, dextrin and cellulose, (CjHjoOj), in which n > 4, are typical polysaccharides. 

The simple sugars or monosaccharides are polyhydroxy aldehydes or ketones, and belong to Solubility Group II. They are termed tetroses, pentoses, hexoses. etc. according to the number of carbon atoms in the long chain constituting the molecule, and aldoses or ketoses if they are aldehydes or ketones. Most of the monosaccharides that occur in nature are pentoses and hexoses. 

Over 200 different monosaccharides are known They can be grouped according to the number of carbon atoms they contain and whether they are polyhydroxy aide hydes or polyhydroxy ketones Monosaccharides that are polyhydroxy aldehydes are called aldoses, those that are polyhydroxy ketones are ketoses Aldoses and ketoses are further classified according to the number of carbon atoms m the mam chain Table 25 1 lists the terms applied to monosaccharides having four to eight carbon atoms... 

Isomerization. Both the carbonyl group and the adjacent hydroxyl group are involved in isomerization of monosaccharides. This reaction can be catalyzed by either a base or an enzyme. By this reaction, an aldose is converted into another aldose and a ketose, and a ketose is converted into two... 

In a similar manner, ketones can react with alcohols to form hemiketals. The analogous intramolecular reaction of a ketose sugar such as fructose yields a cyclic hemiketal (Figure 7.6). The five-membered ring thus formed is reminiscent of furan and is referred to as a furanose. The cyclic pyranose and fura-nose forms are the preferred structures for monosaccharides in aqueous solution. At equilibrium, the linear aldehyde or ketone structure is only a minor component of the mixture (generally much less than 1%). 

The generic term monosaccharide (as opposed to oligosaccharide or polysaccharide) denotes a single unit, without glycosidic connection to other such units. It includes aldoses, dialdoses, aldoketoses, ketoses and diketoses, as well as deoxy sugars and amino sugars, and their derivatives, provided that the parent compound has a (potential) carbonyl gTOup. 

Monosaccharides with an aldehydic carbonyl or potential aldehydic carbonyl group are called aldoses those with a ketonic carbonyl or potential ketonic carbonyl group, ketoses. 

Monosaccharides containing a (potential) aldehydic group and a (potential) ketonic group are called ketoaldoses (see 2-Carb-12) this term is preferred to the alternatives on the basis of 2-Carb-2.1.1 (aldose preferred to ketose). 

The basis for the name is the structure of the parent monosaccharide in the acyclic form. Charts I and IV (2-Carb-10) give trivial names for parent aldoses and ketoses with up to six carbon atoms. 2-Carb-8.2 and 2-Carb-10.3 describe systematic naming procedures. 

Note 2. Since all aldoses up to the hexoses have trivial names that are preferred, the systematic names apply only to the higher aldoses. However, the configurational prefixes are also used to name ketoses (see below) and other monosaccharides. 

An intramolecular ether (commonly called an intramolecular anhydride), formally arising by elimination of water from two hydroxy groups of a single molecule of a monosaccharide (aldose or ketose) or monosaccharide derivative, is named by attaching the (detachable) prefix anhydro- preceded by a pair of locants identifying the two hydroxy groups involved. 

Monosaccharides are those carbohydrates that cannot be hydrolyzed into simpler carbohydrates They may be classified as trioses, tetroses, pentoses, hex-oses, or heptoses, depending upon the number of carbon atoms and as aldoses or ketoses depending upon whether they have an aldehyde or ketone group. Examples are listed in Table 13-1. 

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