2-Fluoro-6-pyridinyloxy derivatives of 2-ethoxyvinyl carbinols react with radicals derived from xanthates by an addition–fragmentation pathway to give highly functionalized ketones after acid hydrolysis. 1, 4-Diketones are readily accessible by this approach. α, β- Unsaturated ketones can be obtained by starting with geminal acetoxy xanthates prepared by addition of a simpler xanthate to vinyl acetate.