New chemistry and stereochemistry of tricoordinate phosphorus esters containing phosphorus–fluorine bond

Abstract

The use of O-arylphosphoroamidites in the synthesis of nucleosides phosphates of biological interest and their P–F analogues is described. This goal is achieved by extremely smooth reaction of O-arylphosphites with fluoride anion donors. Dinucleoside phosphorofluoridites RO(R′O)PF prepared by this method can be resolved into diastereoisomeric forms. Phosphorofluoroamidites –P(F)NR 2 are efficient reagents in the synthesis of corresponding esters –P(F)OR′. These P(III)–F systems are employed in a new and effective synthesis of trifluoromethylphosphonite P(III)–CF 3 by reaction with (trifluoromethyl)trimethylsilane (CF 3SiMe 3). This reaction, catalysed by the fluoride anion, can be part of a sequential procedure that combines formation of P(III)–F compounds with their transformation into the corresponding P(III)–CF 3 system. To cite this article: J. Michalski et al., C. R. Chimie 7 (2004) .