Fluorination of trimethylsilyl phosphites and their structural analogues by sulfuryl chloride fluoride: simple preparation of phosphorofluoridates and related compounds, including deoxynucleoside phosphorofluoridates

Abstract

Trimethylsilyl esters of general formula RR′POSiMe₃ react in a quantitative and fully chemoselective way with sulfuryl chloride fluoride, ClSO₂F, under extremely mild conditions to give phosphorofluoridates RO(R′O)P(O)F of high purity. This work provides easy access to all type of fluoridates from non-toxic starting materials. The synthetic usefulness of this method is illustrated by the synthesis of 3′- and 5′-mononucleoside phosphorofluoridates 10 and 3′,5′-dinucleoside phosphorofluoridates 11 from the corresponding nucleoside trimethylsilyl phosphites.