Chemodivergence between Electrophiles in Cross-Coupling Reactions

Chemodivergent cross-couplings are those in which either one of two (or more) potentially reactive functional groups can be made to react based on choice of conditions. In particular, this review focuses on cross-couplings involving two different (pseudo)halides that can compete for the role of the electrophilic coupling partner. The discussion is primarily organized by pairs of electrophiles including chloride vs. triflate, bromide vs. triflate, chloride vs. tosylate, and halide vs. halide. Some common themes emerge regarding the origin of selectivity control. These include catalyst ligation state and solvent polarity or coordinating ability. However, in many cases, further systematic studies will be necessary to deconvolute the influences of metal identity, ligand, solvent, additives, nucleophilic coupling partner, and other factors on chemoselectivity.