21056-54-2

Upstream product

• 97-30-3 methyl-alpha-D-glucopyranoside 
• 98-88-4 benzoyl chloride 
• 380430-53-5 2-(ethoxycarbonyl)phenylboronic acid 
• 4056-12-6 methyl 4,6-O-(phenylborylene)-α-D-glucopyranoside 
• 33535-04-5 methyl 3-O-benzoyl-4,6-O-benzylidene-α-D-glucopyranoside 
• 3162-96-7 4,6-O-benzylidene-1-O-methyl-α-D-glucopyranoside 

Relevant academic research and scientific papers

Lead-Catalyzed Aqueous Benzoylation of Carbohydrates with an Acyl Phosphate Ester

Biochemical systems utilize adenylates of amino acids to aminoacylate the 3′-terminal diols of tRNAs. The reactive acyl group of the biological acylation agent is a subset of the general class of acyl phosphate monoesters. Those compounds are relatively stable in aqueous solutions, and their alkyl esters are conveniently prepared. It has previously been shown that biomimetic reactions of acyl phosphate monoesters with diols and carbohydrates are promoted by lanthanide salts. However, they also promote hydrolysis of acyl phosphate reagents, and the overall yields are modest. An assessment of the catalytic potential of alternative Lewis acids reveals that lead ions may be more effective as catalysts than lanthanides. Treatment of carbohydrates with benzoyl methyl phosphate (BMP) and triethylamine in water with added lead nitrate produces monobenzoyl esters in up to 75% yield. This provides a water-compatible pathway for novel patterns of benzoylation of polyhydroxylic compounds.

Highly Regioselective Monoacylation of Unprotected Glucopyranoside Using Transient Directing-Protecting Groups

The regioselective functionalization of monosaccharides is notoriously achieved using metal catalysis, lengthy synthetic strategies requiring protection/deprotection, various enzymes, or other methods that target cis-diols (and thus cannot be used with glucopyranose derivatives), In this paper, we report a new method using selected boronic acids as temporary protecting groups, and describe its application to the regioselective functionalization of methyl α-d-glucopyranoside, the most difficult monosaccharide to functionalize regioselectively. Generally, reactions of glucopyranosides may lead to a plethora of mono- and polyfunctionalized derivatives, yet our method gave the 3-O-acetylated, 2-O-benzoylated, and 2-O-pivaloylated derivatives of methyl α-d-glucopyranoside as major products. We focused on the use of recyclable and green temporary protecting groups (in a one-pot reaction) and on the modulation of the intramolecular hydrogen-bonding network using selected arylboronic acids. A complete scalable procedure leading to a single regioisomer from unprotected methyl α-d-glucopyranoside is presented.