Mild Copper-Catalyzed Vinylation Reactions of Azoles and Phenols with Vinyl Bromides

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 with 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. The corresponding N‐(1‐alkenyl)azoles and alkenyl aryl ethers are obtained in high yields and selectivities under 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 on a laboratory scale and easily adaptable to an industrial scale, is very competitive compared to the existing methods that allow the synthesis of such compounds. Coupling with copper: Vinylation of mono‐, di‐, and triazoles and phenol derivatives with vinyl bromides can be efficiently performed by means of catalytic amounts of copper iodide and inexpensive nitrogen ligands 1 or 2. The reaction is applicable to a wide range of substrates and proceeds at very mild temperatures (35–110 °C). N‐(1‐alkenyl)azoles and alkenyl aryl ethers are obtained in high yields and selectivities through this practical protocol, which can easily be adapted for industrial applications.