Sulfanyl- and selanyldifluoromethylphosphonates as a source of phosphonodifluoromethyl radicals and their addition onto alkenes.

[figure: see text] Two different strategies are shown to produce sulfanyl and selanyldifluoromethylphosphonates. Thus, treatment of sulfanyldichloromethylphosphonates by 3HF.NEt3 in the presence of zinc bromide produces the corresponding sulfanyldifluoromethylphosphonates. In addition, lithiation of difluoromethylphosphonates followed by quenching with phenylsulfanyl chloride, phenylselanyl chloride, or diphenyl diselenide yields the corresponding sulfanyl- and selanyldifluorophosphonates. Generation of phosphonodifluoromethyl radicals from such precursors in the presence of alkenes produces the expected adducts.