Novel reactions with the underutilized BrF3 - The chemistry with nitriles

Bromine trifluoride is a relatively new reagent in organic and fluoroorgani c chemistry. Under the right conditions, it can be a useful tool and genera te new types of reactions and compounds. In order to react properly, it has to be complexed by at least two, close in space, electron donating element s, after which it's nucleophilic fluorides can react with nearby potential electrophiles. Thus, it was found that while BrF3 does not react cleanly wi th aliphatic nitriles, it can convert them with good yield to a trifluorome thyl group when a neighboring carboxylic moiety is present. BrF3 attacks al so the electrophilic. carbonyl carbon transforming it to a difluoroether, b ut simple hydrolysis regenerates the carboxylic. group to give eventually a -trifluoromethyl esters (e.g. 5 --> 6). In the case of the keto nitrile 14, a participation of the internal nucleophilic oxygen in attacking the nitri le carbon was also observed. (C) 2001 Elsevier Science B.V. All rights rese rved.