American Chemical Society
jo7b03142_si_001.pdf (2.21 MB)

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

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journal contribution
posted on 2018-01-25, 00:00 authored by Yuyang Li, Ronald Kluger
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.