Selective Denitrificative Fluorination and Desulfurative Fluorination Controlled by AgF/AgF2

Abstract

Abstract The development of novel N-fluoroalkylated phosphoramidates will enrich the toolbox of organophosphorus chemistry. Here, we report the synthesis of [19F]/[18F] phosphoramidofluoridates and N-CF3 phosphoramidates via two controllable fluorinations of phenyl phosphorylcarbamodithioate (substrate S): S underwent selective P–N bond cleavage to access phosphoramidofluoridates by silver(I) fluoride and successive desulfurative fluorination to access N-CF3 phosphoramidates by silver(II) fluoride. Moreover, the desulfurative fluorination strategy can be extended to the preparation of N-CF2H, N-C2F5, and N-CF2OPh phosphoramidates.