Synthesis 2019; 51(20): 3784-3791
DOI: 10.1055/s-0037-1611907
short review
© Georg Thieme Verlag Stuttgart · New York

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

Yuyang Li
,
Ronald Kluger
Department of Chemistry, University of Toronto, 80 St. George Street, Toronto, ON, M5S 3H6, Canada
› Author Affiliations
Supported by a Discovery Grant from the Natural Sciences and Engineering Research Council of Canada (Grant/Award No: A9918).
Further Information

Publication History

Received: 08 May 2019

Accepted after revision: 19 July 2019

Publication Date:
12 August 2019 (online)


Abstract

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