Oxidatively Catalyzed Nucleophilic Aromatic Substitution. Further Studies on the SON2 Reaction

Article abstract of DOI:10.1021/jo00192a017

The oxidation of several electron-rich fluoroarenes in the presence of nucleophile, usually acetate ion, has been investigated.Two substrates, 1- and 2-fluoronaphthalene, have been shown to undergo formally nonoxidative fluorine/acetoxy exchange induced by chemical oxidants such as benzoyl peroxide, potassium peroxydisulfate, and copper(III).The mechanism is believed to involve electron-transfer chain catalysis according to the S_ON2 mechanism.On electrochemical oxidation of these substrates, the major pathway observed was oxidative substitution of hydrogen.The catalytic efficiency of the anodically initiated title reaction is also improved at higher temperatures; e.g., anodic acetoxydefluorination of 4-fluoroanisole takes place with a current efficiency of 590percent at 78 deg C.We also give the first example of an intramolecular although not catalytic S_ON2 reaction.