The use of methyl 2,2-difluoro-2-(fluorosulfonyl)acetate as the difluorocarbene source to generate an in situ source of difluoromethylene triphenylphosphonium ylide

• Methyl 2,2-difluoro-2-(fluorosulfonyl)acetate is a good source of difluorocarbene.
• The difluorocarbene generated by MDFA combines with triphenylphosphine to form difluoromethylene triphenylphosphonium ylide.
• The ylide reacts with aldehydes and ketones to form 1,1-difluoroalkenes.
• Calculations show that the binding of the difluorocarbene and triphenylphosphine in the ylide is weak.

Under moderate conditions in the presence of a demethylating reagent, such as iodide, methyl 2,2,-difluoro-2-(fluorosulfonyl)acetate (MDFA) releases difluorocarbene, which in the presence of triphenylphosphine forms difluoromethylene triphenylphosphonium ylide. When the process is carried out also in the presence of aldehydes or activated ketones, the ensuing in situ Wittig-type reaction of the ylide with the carbonyl reactants produces 1,1-difluoroalkenes in good yield. Density Functional Theory calculations were used to provide new estimates of the energies and structures of singlet and triplet states of CH2:, CHF:, and CF2: carbenes, as well as those of their respective triphenylphosphonium ylides.

1,1-Difluoroalkenes are formed using a new source of difluoromethylene triphenylphosponium ylide.Figure optionsDownload as PowerPoint slide