Recent Advances in Pd‐catalyzed Suzuki‐Miyaura Cross‐Coupling Reactions with Triflates or Nonaflates

The Pd‐catalyzed Suzuki‐Miyaura (SM) cross‐coupling of organo halides with organoboron compounds is a widely used tool in organic synthesis for the construction of C‐C bonds. Alternative methods using pseudohalides, such as triflates or nonaflates, are also suitable for this transformation. These substrates offer the advantages of simple access from readily available phenols (or enolizable ketones) and possible use for chemodivergent sequential SM couplings using electronically differentiated leaving groups. This review aims to give an overview about the current strategies of Suzuki‐Miyaura cross‐couplings with triflates or nonaflates as leaving groups. In particular, it aims to give a better understanding about the development of new efficient catalyst systems over the last decade overcoming the limitations of the standard catalyst Pd(PPh3)4. The hydrolysis of triflates as a common side reaction and its prevention will be discussed, as well as the possible transformation of triflates into halides as a strategic alternative. A matrix table is provided to guide the practitioners to find suitable reaction conditions for the various combinations of aryl/enol triflate substrates and arylboronic acids with differing electronic character.