Metal-Catalyzed Site-Selective Monoacylation of Diols in Aqueous Media

Site-selective reactions of water-soluble biomolecules are being developed to produce efficient conversions in water and water-/solvent mixtures. This review focuses on the use of designs based on bis-bidentate chelation of large metal ions by diols to be acylated by a co-chelated water-stable reagent. Topics discussed include: 1. The preparation and properties of water-stable acyl phosphate monoesters and their reactions with diol-chelated metal ions. 2. Site-selective monoaminoacylation of 3 '-terminal diols of RNA and their applications in protein engineering. 3. Site-selective monoacylation of sugars with acyl phosphate monoesters associated with metal ions, including lanthanum and lead. The combination of metal ion, 1,2-diol, and acyl phosphate monoester produces site-selective reactions in aqueous media- that can produce a general approach to site-selective mono-(amino)acylation in RNA and carbohydrates. 1 Introduction 2 Synthetic Aminoacylation of tRNA 3 Activated Amino Acids in Water 4 Metal Ions and Their Effects on the Reactivity of Acyl Phosphate Monoesters 5 The Challenge of Site-Selective Acylation of Carbohydrates in Water 6 Conclusions and Prospects