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The addition of diethyldifluoromethylphosphonate to LDA containing cerium(III) chloride in THF generates an organometallic nucleophile that reacts efficiently with esters and DMF (1,2-addition) affording moderate to good yields of adducts, and extending considerably the range of compounds available containing the difluoromethylenephosphonate group.

The cerium-mediated reaction between lithio (diethyldifluoromethyl)-phosphonate 2 proceeds smoothly to afford good yields of ketophosphonates; the reaction with DMF led to the formation of the corresponding aldehyde which was isolated as a hydrate with interesting and useful properties.

New dienophiles containing the difluoromethylenephosphonato group are synthesised from readily-available starting materials and cycloadditions with reactive dienes are executed successfully.

The cerium(III)-mediated addition of diethyl (lithiodifluoromethyl)phosphonate to a benzoquinone monoketal allows the synthesis of phenol bearing the (diethoxyphosphonyl)difluoromethyl group via short, scaleable reaction sequences which avoid the use of the DAST reagent.

The cerium-mediated reaction between lithio (diethyldifluoromethyl)-phosphonate 2 proceeds smoothly to afford good yields of ketophosphonates; the reaction with DMF led to the formation of the corresponding aldehyde which was isolated as a hydrate with interesting and useful properties.

New dienophiles containing the difluoromethylenephosphonato group are synthesised from readily-available starting materials and cycloadditions with reactive dienes are executed successfully.