| Sumario: | Simple aluminosilicates, including NaX and NaY zeolites, catalyze the selective halogen exchange reaction between two different alkyl organohalides, either in batch or in flow, without any additive or solvent, by simply heating at 130 °C and with <5 wt% of solid catalyst. The reaction protocol tolerates different functional groups and gives two new organohalides in good yields. Mechanistic studies unveil the key role of the zeolite oxygen atoms and countercations, to trigger the heterolytic scission of the R–X bond and generate intermediate alkoxy and halide species, respectively, which recombine within the zeolite framework. These results open a new way to synthesize organohalides with simple solid catalysts and expand the use of aluminosilicates in organic synthesis.
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