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

摘要

The use of Oarylphosphoroamidites 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 Oarylphosphites with fluoride anion donors.Dinucleoside phosphorofluoridites RO(R'O)PF prepared by this method can be resolved into diastereoisomeric forms.Phosphorofluoroam-idites-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.