Ch. 27 - Carbohydrates, Nucleic Acids, and Lipids

Mullins - Organic Chemistry: A Learner Centered Approach 1st Edition

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Mullins 1st Edition

Ch. 27 - Carbohydrates, Nucleic Acids, and Lipids

Problem 22

Chapter 26, Problem 22

Suggest a mechanism by which α-d-glucopyranose is converted to β-d-glucopyranose in acid. [See Figure 27.18.]

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Identify the starting and ending structures: α-d-glucopyranose and β-d-glucopyranose. Notice that the difference is the position of the hydroxyl group at the anomeric carbon (C1), which is axial in α and equatorial in β.

Recognize that the conversion involves the opening of the pyranose ring to form the open-chain form of glucose, followed by reclosure to form the β-anomer.

In acidic conditions, the reaction begins with the protonation of the oxygen in the hemiacetal linkage of α-d-glucopyranose, making it a better leaving group.

The ring opens to form the open-chain form of glucose, which is an aldehyde. This step involves the breaking of the C1-O bond, resulting in a linear form of glucose.

The open-chain form can then undergo ring closure again, but this time the hydroxyl group can attack the carbonyl carbon from the opposite side, leading to the formation of β-d-glucopyranose, where the hydroxyl group at C1 is now equatorial.

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Key Concepts

Here are the essential concepts you must grasp in order to answer the question correctly.

Anomeric Carbon

The anomeric carbon is the carbon atom in a sugar that is derived from the carbonyl carbon of the open-chain form. In cyclic sugars, it is the carbon that determines the alpha (α) or beta (β) configuration based on the orientation of the hydroxyl group. Understanding the role of the anomeric carbon is crucial for explaining the interconversion between α-d-glucopyranose and β-d-glucopyranose.

Acid-Catalyzed Equilibrium

In an acid-catalyzed reaction, the presence of acid facilitates the conversion between different forms of a compound by protonating functional groups, making them more reactive. For the conversion of α-d-glucopyranose to β-d-glucopyranose, the acid helps to open the cyclic structure, allowing the molecule to equilibrate between its anomeric forms before closing again in the β configuration.

Mutarotation

Mutarotation is the process by which the specific rotation of a carbohydrate changes over time as it equilibrates between its anomeric forms. In the case of α-d-glucopyranose and β-d-glucopyranose, mutarotation involves the interconversion of these two forms in solution, which is facilitated by the presence of acid, leading to a dynamic equilibrium between the two anomers.

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Mechanism

Related Practice

Textbook Question

Which of the following molecule pairs are epimers?

(a)

(b)

(c)

Textbook Question

Suggest a mechanism by which α-d-glucopyranose is converted to β-d-glucopyranose in base. [See Figure 27.18.]

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Textbook Question

Using the Haworth projection, draw the furanose ring that would form between the C₅ hydroxyl group and the ketone at C₂ for the molecule shown.

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Textbook Question

Using the Haworth projection, draw the furanose ring that would form between the C₄ hydroxyl group and the aldehyde at C₁ for the molecule shown.

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Textbook Question

Draw the α- and β-anomers of d-mannofuranose. [The structure of mannose is in Figure 27.11.]

Textbook Question

Draw the α- and β-anomers of d-talopyranose. [The structure of talose is in Figure 27.11.]

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