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.