Palladium-Catalyzed Amination of Aryl Triflates and Importance of Triflate Addition Rate

We report that a combination of DPPF (1,1-bis(diphenylphosphino)ferrocene) and Pd(dba)2 leads to the amination of aryl triflates, a reaction that allows for the conversion of phenols to arylamines. A combination of BINAP and Pd(dba)2 also catalyzes the amination of aryl triflates, but P(o-tolyl)3 complexes were not effective catalysts. In some cases, slow addition of the aryl triflate was necessary to prevent cleavage of the triflate and generation of phenol. We found that added halide, necessary in some cross-coupling chemistry of aryl sulfonates, was an unnecessary additive and even inhibited the amination chemistry.