Rationally designed squaryldiamides - a novel class of sugar-nucleotide mimics?

Org Biomol Chem. 2010 Aug 7;8(15):3488-99. doi: 10.1039/c004165c. Epub 2010 Jun 7.

Abstract

Sugar-nucleotides such as GDP-mannose, GDP-fucose and UDP-glucose are important biomolecules with a central role in carbohydrate and glycoconjugate biosynthesis, metabolism and cell signalling. Analogues and mimics of naturally occurring sugar-nucleotides are sought after as chemical tools and inhibitor candidates for sugar-nucleotide-dependent enzymes including glycosyltransferases. Many sugar-nucleotides bind to their target glycosyltransferases via coordination of the diphosphate group to a divalent metal cofactor in the active site. The identification of uncharged, chemically stable surrogates for the diphosphate group, with the ability to coordinate to a divalent metal, is therefore an important design criteria for the development of sugar-nucleotide mimics. Here, we describe the rational design and synthesis of a novel class of sugar-nucleotide mimics based on a squaryldiamide scaffold, an uncharged phosphate isostere. We demonstrate by comprehensive NMR titration experiments that the new sugar-nucleotide mimics coordinate efficiently to Mg(2+), and provide results from biological studies with a therapeutically relevant mannosyltransferase from Trypanosoma brucei. Our findings suggest that squaryldiamides are a promising template for the development of sugar-nucleotide mimics, and illustrate the considerable potential of the squarylamide group as a fragment for inhibitor design.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Antiprotozoal Agents / chemical synthesis
  • Antiprotozoal Agents / chemistry
  • Antiprotozoal Agents / pharmacology
  • Biomimetic Materials / chemical synthesis
  • Biomimetic Materials / chemistry*
  • Biomimetic Materials / pharmacology
  • Cyclobutanes / chemical synthesis
  • Cyclobutanes / chemistry*
  • Cyclobutanes / pharmacology
  • Drug Design*
  • Magnesium / chemistry
  • Magnetic Resonance Spectroscopy
  • Mannosyltransferases / antagonists & inhibitors
  • Nucleotides / chemistry*
  • Sulfonamides / chemical synthesis
  • Sulfonamides / chemistry*
  • Sulfonamides / pharmacology
  • Trypanosoma brucei brucei / enzymology

Substances

  • Antiprotozoal Agents
  • Cyclobutanes
  • Nucleotides
  • Sulfonamides
  • squaric acid amide
  • Mannosyltransferases
  • dolichyl-phosphate beta-D-mannosyltransferase
  • Magnesium