We describe how the merger of deprotonation, halogenation, and substitution into compatible processes enables the productive functionalization of traditionally unstable carbanionic intermediates. This strategy enables the first oxidative coupling protocol of α,α-difluorobenzylic C─H bonds with heteronucleophiles. Here, transiently generated α,α-difluorobenzylic carbanionic intermediates undergo halogen transfer from 2-bromothiophenes to form electrophilic ArCF