Dimethylzinc-Initiated Radical Coupling of β-Bromostyrenes with Ethers and Amines.

A new coupling reaction has been developed in which β-bromostyrenes react with ethers and tertiary amines to introduce the styryl group in the α-position. The transformation is mediated by Me2 Zn/O2 with 10 % MnCl2 and is believed to proceed by a radical addition-elimination mechanism. The ether and the amine are employed as solvent and the coupling takes place through the most stable α radical for unsymmetrical substrates. The products are obtained in moderate to good yields as the pure E isomers. The coupling can be achieved with a range of smaller cyclic and acyclic ethers/amines as well as various substituted β-bromostyrenes.