A Rh‐catalyzed divergent alkylation of indole derivatives with vinyl carbonate was described. Depending on the substrate and solvent, indoles reacted with vinyl carbonate and alcohols to give C2 carboxymethylated adducts via a sequential three‐component reaction, while indolines reacted with vinyl carbonate in toluene to provide C7 formylmethylated products. The structures of carboxymethylated product 3 a and formylmethylated product 5 a were further confirmed by X‐ray analysis. The current protocol featured broad substrate scope, tunable reaction conditions, divergent functionalization, and good regioselectivity.

A regioselective arylation of aliphatic N-fluorosulfonamides with imidazopyridines enabled by breaking of N–F and α C­(sp3)–H bond to form C–N and C–C bonds was described. With CuCl as the catalyst, a radical mechanism was proposed to produce N-arylated aliphatic sulfonamides via a N radical intermediate. Importantly, under acidic conditions, an in situ generated imine was the possible intermediate, which was trapped by imidazopyridines to form α C­(sp3)–H arylated aliphatic sulfonamides. The current protocol featured a broad substrate scope, tunable reaction conditions, operational convenience, and good regioselectivity.

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