Palladium-catalyzed oxidative aminofluorination of styrenes

Abstract

A novel palladium-catalyzed intermolecular aminofluorination of styrenes has been developed, using silver fluoride as the fluorine source, palladium diacetate as metal catalyst, and acetonitrile as solvent at room temperature. As regard to the mechanism, we proposed that the anti-Markovnikov aminopalladation was involved in the construction of C-N bond. This selectivity of nucleophilic palladation of styrenes is different from that reported before. In order to verify our proposed mechanism, we conducted the competition experiments using styrenes containing different functional groups. The results are consistent with our analysis. We belive that the C-F bond is formed after the Pd (II)-C is oxidized to Pd (IV)-C. Namely, the high oxidative state palladium is involved in catalytic cycle. In all, this transformation represents a novel strategy to synthesize a variety of vicinal fluoroamine derivatives. © 2012 Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences.