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The copper‐ and palladium/copper‐catalyzed direct C–H fluoroalkenylation of pyridine N‐oxides and related heterocycles using various gem‐bromofluoroalkenes as electrophiles is reported. The dimetallic palladium/copper process proved to be more efficient than copper catalysis, giving access to various relevant 2‐fluoroalkenylated azines.
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