The domino C–H/N–H allylation of aryl imidates was accomplished by a versatile cobalt­(III) catalyst. In contrast to a tandem rhodium/palladium catalysis approach, an operationally simple cationic cobalt complex proved effective in the step-economical C–H/N–H functionalization of imidates to directly provide expedient access to decorated vinyl isoquinolines by kinetically relevant C–H activation.

The late-stage modification of structurally complex peptides bears great potential for drug discovery, crop protection, and the pharmaceutical industry, among others. Whereas traditional approaches largely rely on prefunctionalizations, C-H activation catalysis has in recent years emerged as an increasingly powerful tool for post-translational peptide modifications in a step-economic manner. Herein, we summarize recent progress in organometallic C-H activation on peptides until June 2018, including position- and chemoselective palladium-, ruthenium-, and manganese-catalyzed processes.

After a brief introduction emphasizing the synthetic relevance of the allylic C–H activation step, evoking the first pioneering stoichiometric studies that sowed the “seeds” of this subject, and analyzing similarities and differences between a “classical” and a “direct” Pd‐catalyzed allylation process, this review outlines some selected examples of palladium‐catalyzed direct allylic functionalization. This old reaction, ignored for many years, is now living a new and exciting era.