A new and efficient Ag‐catalyzed method for the nitration of anilides by using sodium nitrite as a cheap and available NO2 source has been developed. This C–H functionalization reaction is ortho‐selective, achieves moderate to high yields and shows excellent functional group tolerance. Furthermore, it provides a novel approach to ortho‐nitrated anilides, which are very tricky to access with traditional methods.

A RuII‐catalyzed highly regioselective C–H acyloxylation of azoarenes with inexpensive alkyl and aryl carboxylic acids as an acyloxylation agent is described. The reaction demonstrates a broad substrate scope and good functional group tolerance. This method provides a facile procedure to synthesize ortho‐acyloxylated azoarene derivatives.