Design and evolution of copper apatite catalysts for N-arylation of heterocycles with chloro- and fluoroarenes

We report the preparation of recyclable heterogeneous catalysts, copper-exchanged fluorapatite, and copper-exchanged tert-butoxyapatite by incorporating basic species F-/tBuO- in apatite in situ by coprecipitation and subsequent exchange with Cu(II). These basic copper catalysts catalyzed N-arylation of imidazoles and other heterocycles with chloroarenes and electron-poor fluoroarenes in good to excellent yields. Synthesis and characterization of some of the intermediates of the catalytic cycle gave some insight into the mechanism of the very important organic transformation. The necessity of basic sites for the activation of C-Cl and C-F bonds in the N-arylation of heterocycles with haloarenes is well-established. Copyright © 2005 American Chemical Society.