Introduction　of　fluorine　atoms　or　fluorine-containing　moieties　into　organic　molecules　can　dramatically　influence　their　properties,　thereby　increasing　their　applicability　as　drugs　or　building　blocks　for　organic　materials.　Herein,　we　report　intriguing　fluorinating　electrophilic　interception　achieving　the　synthesis　of　various　fluorine-containing　compounds　where　oxidation　or　protodeboronation　of　alkenyl　boron　species　from　1,2-migration　of　alkynyl　tetracoordinate　borons　were　involved.　Obviously,　α,α-difluoroketones　are　readily　accessible　within　30　min,　which　might　provide　an　alternative　approach　to　[18F]α,α-difluoroketones.　Meanwhile,　versatile　monofluoroalkenes,　α-SCF3　ketones,　and　(highly　deuterated)　SCF3-containing　alkenes　can　be　assembled　in　good　yields　via　this　strategy.　This　protocol　features　tunable　synthesis,　high　stereoselectivity　and　efficiency,　applicability　to　late-stage　modifications　of　bioactive　molecules,　and　modular　introduction　of　fluorine　atoms/fluorinated　groups.　Additionally,　these　transformations　can　perfectly　suppress　the　Zweifel　pathway　and　keep　the　fluorine　atoms/fluorinated　groups　intact　without　elimination,　and　the　difluoropiperidine　scaffolds　could　also　be　forged　efficiently　via　this　protocol.　©　2024　Elsevier　Inc.