Hemiacetals in Carbohydrate Chemistry

The normal form of most sugars is in a cyclic hemiacetal form.  The preferred form varies from sugar to sugar:  some prefer to be a 6-member ring "pyranose", like glucose:


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Others, like ribose and fructose, prefer the 5-member ring "furanose" form.

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An important aspect of hemiacetal formation is the production of a new stereocenter at the carbonyl carbon.  This is called the anomeric position.  In general, both possible isomers are formed.  However, the two diastereomers can often be separated.  The β-form of D-glucose crystallizes, but after redissolving the pure β form in water it reconverts to an equilibrium mixture of the two anomeric forms; this process is called mutarotation because it can be detected by a change in the optical rotation.

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Further evidence of the interconversion of open and closed forms is seen in the capacity of aldoses to react with reagents that only attack aldehudes. See Section 24-4 and the discussion of reducing vs. nonreducing sugars; Section 24-6 on the reduction to alditols is another example.