Reported herein is an unprecedented synthesis of C3-fluorinated oxindoles through cross-dehydrogenative coupling of C(sp )-H and C(sp )-H bonds from malonate amides. Under the unique and mild electrochemical conditions, the requisite oxidant and base are generated in a continuous fashion, allowing the formation of the base- and heat-sensitive 3-fluorooxindoles in high efficiency with broad substrate scope. The synthetic usefulness of the electrochemical method is further highlighted by its easy scalability and the diverse transformations of the electrolysis product.

Transition metal catalyzed C−H phosphorylation remains an unsolved challenge. Reported methods are generally limited in scope and require stoichiometric silver salts as oxidants. Reported here is an electrochemically driven RhIII‐catalyzed aryl C−H phosphorylation reaction that proceeds through H2 evolution, obviating the need for stoichiometric metal oxidants. The method is compatible with a variety of aryl C−H and P−H coupling partners and particularly useful for synthesizing triarylphosphine oxides from diarylphosphine oxides, which are often difficult coupling partners for transition metal catalyzed C−H phosphorylation reactions. Experimental results suggest that the mechanism responsible for the C−P bond formation involves an oxidation‐induced reductive elimination process.

Dehydrogenative annulation under oxidizing reagent-free conditions is an ideal strategy to construct cyclic structures. Reported herein is an unprecedented synthesis of pyrrolidine and tetrahydropyridine derivatives through electrochemical dehydrogenative annulation of N-allyl amides with 1,3-dicarbonyl compounds. The electrolytic method employs an organic redox catalyst, which obviates the need for oxidizing reagents and transition-metal catalysts. In these reactions, the N-allyl amides serve as a four-atom donor to react with dimethyl malonate to give pyrrolidines by a (4+1) annulation, or with β-ketoesters to afford tetrahydropyridine derivatives by a (4+2) annulation.