A difluorosulfide as a Freon-free source of phosphonodifluoromethyl carbanion.
The synthesis of difluoromethylphosphonates is becoming difficult due to environmental protective laws restricting the use of HCFCs and CFCs as starting chemicals. To circumvent this limitation, we report the preparation of a thioether as a new source of the lithiodifluoromethylphosphonate. This methodology avoiding the use of HCFCs involves a selective fluorination of sulfide followed by a thiaphilic addition of an organometallic reagent, which offers an alternative route to obtain phosphonodifluoromethyl carbanion. A contrasted reactivity, due to a medium effect, was also noted which allows addition of a wide range of electrophiles including nitroalkenes and DMF to thioethers.
Henry-dit-Quesnel
Arnaud
A
Laboratoire de Chimie Moléculaire et Thioorganique, UMR CNRS 6507, Université de Caen, ENSI Caen 6 Bd du Maréchal Juin, F 14050 Caen, France.
Toupet
Loic
L
Pommelet
Jean-Claude
JC
Lequeux
Thierry
T