From ketones, aldehydes or alkyl halides to terminal 1,1-difluoroolefins using BrF3

Terminal difluoromethylenes were prepared by two different routes: (a) by treating ketones and aldehydes with bis(methylthio)methane, producing 2-alkyl-1,1-bis(methylthio)alkene (2) (b) reacting alkyl halides with tris(methylthio)methane forming 1-alkyl-1,1,1-tris(methylthio)alkane derivatives (7). The reaction of either 2 or 7 with BrF3, followed by oxidation with HOF·CH3CN gave the difluorosulfonyl derivatives 4. Consecutive treatment with Zn led to the target difluoroolefins (5) in overall yields of 60–75%.