Acyl Group Migration in Pyranosides as Studied by Experimental and Computational Methods

Area of Science:

• Carbohydrate Chemistry
• Organic Chemistry
• Physical Organic Chemistry

Background:

• Acyl group migration impacts acylated organic compounds, especially carbohydrates, affecting synthesis and purification.
• Previous studies on acyl migration were isolated, lacking comprehensive analysis across different monosaccharides under uniform conditions.

Purpose of the Study:

• To comprehensively investigate acyl migration in various monosaccharides using diverse acyl groups.
• To elucidate the factors influencing acyl migration rates and mechanisms.

Main Methods:

• Experimental studies combined with kinetic analysis.
• Theoretical computational tools were employed for mechanistic modeling.
• Utilized five different acyl groups across various monosaccharides.

Main Results:

• Monosaccharide anomeric configuration significantly affects acyl migration rates.
• Relative hydroxyl group configurations and acyl group type are also key influencing factors.
• A detailed mechanistic model showed migration proceeds via a stepwise anionic mechanism.

Conclusions:

• Acyl migration mechanism is dependent on hydroxide concentration and hydroxyl group pKa.
• Understanding acyl migration is crucial for efficient carbohydrate synthesis and manipulation.
• The study provides a unified mechanistic framework for acyl migration in monosaccharides.