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 methylvinylketonesinto alpha,alpha-difluorinated cyclopentanones. Initiated by 5 mol % of nBu(4)NBr, the multistep reaction occurred in one pot under mild conditions via the in situ formation of silyl dienol ethers, difltiorncyclo-propanation, thermal vinylcydopropan-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.