An increasing number of biologically active compounds in the pharma and agro-chemical sector contain carbon fluorine bonds. One of the most common methods to introduce fluorine into intermediates is the well-investigated halogen-exchange reaction, in which chloro- and bromoaromatics activated towards nucleophilic substitution, react with a fluoride source to yield the corresponding fluoroarenes. In general, the reaction is supported by phase-transfer catalysts. The use of a new class of very active phase-transfer catalysts gives the possibility of substituting even halogens with weak activation giving a convenient access to interesting compounds that are not available so far and opening up new synthetic routes in Halex chemistry. Our new classes of catalysts, CNC + ( 1a), PNC + ( 2a) and several different approaches presented by other groups are described and experimental results discussed.
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