Trifluoromethylated cyclic-ADP-ribose mimic: synthesis of 8-trifluoromethyl-N(1)-[(5''-O-phosphorylethoxy)methyl]-5'-O-phosphorylinosine-5',5''-cyclic pyrophosphate (8-CF(3)-cIDPRE) and its calcium release activity in T cells

Org Biomol Chem. 2010 Oct 21;8(20):4705-15. doi: 10.1039/c0ob00090f. Epub 2010 Aug 25.

Abstract

A convenient trifluoromethylation method was firstly applied to the synthesis of 8- CF(3)-purine nucleosides. On the basis of this method, new protection and deprotection strategies were developed for the successful synthesis of the trifluoromethylated cyclic-ADP-ribose mimic, 8-CF(3)-cIDPRE 1. Using intact, fura-2-loaded Jurkat T cells compound 1 and 2',3'-O-isopropylidene 8-CF(3)-cIDPRE 14 were characterized as membrane-permeant cADPR agonists. Contrary to the 8-substituted cADPR analogues that mainly act as antagonists of cADPR in cells, 8-substituted cIDPRE derivatives were shown to be Ca(2+) mobilizing agonists. Here we report that even compound 1, the 8-substituted cIDPRE with the strong electron withdrawing CF(3) group, behaves as an agonist in T cells. Interestingly, also the partially protected 2',3'-O-isopropylidene 8-CF(3)-cIDPRE activated Ca(2+) signaling indicating only a minor role for the hydroxyl groups of the southern ribose of cADPR for its biological activity. To our knowledge 8-CF(3)-cIDPRE 1 is the first reported fluoro substituted cADPR mimic and 8-CF(3)-cIDPRE 1 and compound 14 are promising molecular probes for elucidating the mode of action of cADPR.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Adenosine Diphosphate Ribose / chemistry
  • Calcium / metabolism*
  • Cyclic ADP-Ribose / analogs & derivatives*
  • Cyclic ADP-Ribose / chemical synthesis
  • Cyclic ADP-Ribose / chemistry
  • Humans
  • Inosine Monophosphate / analogs & derivatives
  • Inosine Monophosphate / chemistry
  • Structure-Activity Relationship
  • T-Lymphocytes / metabolism*

Substances

  • 8-trifluoromethyl-N1-((5''-O-phosphorylethoxy)methyl)-5'-O-phosphorylinosine-5',5''-cyclic pyrophosphate
  • N(1)-((5''-O-phosphorylethoxy)methyl)-5'-O-phosphorylinosine 5',5''-cyclic pyrophosphate
  • Cyclic ADP-Ribose
  • Inosine Monophosphate
  • Adenosine Diphosphate Ribose
  • Calcium