Gold-Catalyzed Chemoselective Couplings of Polyfluoroarenes with Aryl Germanes and Downstream Diversification

This report describes the chemoselective coupling of polyfluoroarenes with aryl germanes in the presence of aromatic C-I, C-Br, C-Cl, C-OTf, and C-SiMe₃ groups, as well as demonstrates the further downstream diversification to give richly functionalized and highly fluorinated polyarenes. The strategy relies on an in situ Umpolung of the FArH, followed by selective Au^(I)/Au^(III)-catalyzed coupling with electron-poor or -rich aryl germanes, even in the presence of challenging ortho-substituents, and widens the currently available coupling space in oxidative gold catalysis to previously inaccessible electron-poor/electron-poor biaryls.