Me3SiCF2Br-Self-Assisted Domino Reaction: Catalytic Synthesis of α,α-Difluoro­cyclo­pentanones from Methyl­vinyl­ketones

A complete self-assistance strategy based on Me3SiCF2Br was used in the domino conversion of methylvinyl­ketones into α,α-difluorinated cyclopentanones. Initiated by 5 mol % of nBu4NBr, the multistep reaction occurred in one pot under mild conditions via the in situ formation of silyl dienol ethers, difluoro­cyclo­propanation, thermal vinyl­cyclo­propane–cyclo­pentene rearrangement, and desilylation. The process takes advantage of the multitasking capability of Me3SiCF2Br as the difluorocarbene source, a silicon-based transfer agent, and a bromine anion releaser.