Iron-Catalyzed Alkoxyl Radical-Induced C-C Bond Cleavage/ gem -Difluoroalkylation Cascade.

An inexpensive iron-catalyzed alkoxyl radical-induced C-C bond cleavage/ gem -difluoroalkylation cascade is presented. Regulated by the structure of alkoxyl radical precursors, fluorinated distal diketones were synthesized through a ring-opening strategy and difluoroalkylated medium-sized lactones and macrolactones were constructed via a ring-expansion strategy. Both protocols proceeded under mild and redox neutral conditions with a broad substrate scope and good functional group compatibility.