Ligand‐ and Solvent‐Tuned Chemoselective Carbonylation of Bromoaryl Triflates

The palladium‐catalyzed chemoselective carbonylation of bromoaryl triflates is reported. The selective C−Br bond versus C−OTf (OTf=triflate) bond functionalization can be remarkably tuned by the combination of the ligand [4,5‐bis(diphenylphosphino)‐9,9‐dimethylxanthene (Xantphos) vs. 1,1′‐bis(diphenylphosphino)ferrocene (DPPF)] and the solvent (toluene vs. DMSO). The respective ligand and solvent effects are rationalized by DFT calculations. In contrast, the monodentate ligands BuPAd2 and tBu3P prefer the selective C−Br bond activation and are solvent insensitive. Keep control: Palladium‐catalyzed chemoselective carbonylation of bromoaryl triflates is reported. The influencing effects of different solvents (polar vs. non‐polar) and ligands (e.g., monodentate vs. bidentate) on the chemoselectivety is discussed based on experimental observations as well as DFT calculations (see scheme; Xantphos=4,5‐bis(diphenylphosphino)‐9,9‐dimethylxanthene, DPPF=1,1′‐bis(diphenylphosphino)ferrocene).