Abstract
An efficient and straightforward copper-catalyzed method allowing vinylation of N- or O-nucleophiles with di- or trisubstituted vinyl bromides is reported. The procedure is applicable to a broad range of substrates since N-vinylation of mono-, di- and triazoles as well as O-vinylation of phenol derivatives can be performed by the mean of catalytic amounts of copper iodide and inexpensive nitrogen ligands 3 or 8. In the case of more hindered vinyl bromides, the use of the original bidentate chelator 8 was shown to be more efficient to promote the coupling reactions than our key tetradentate ligand 3. Corresponding N-(1-alkenyl)-azoles and alkenyl aryl ethers are obtained in high yields and selectivities in very mild temperature conditions (35-110 °C for N-vinylation reactions and 50-80 °C for O-vinylation reactions). Moreover, to our knowledge, this method is the first example of a copper-catalyzed vinylation of various azoles. Finally, this protocol, practical at the scale of the laboratory and easily adaptable to an industrial scale, is very competitive compared to the whole of existing methods allowing the syntheses of such compounds.