Triethylborane-induced bromine atom-transfer radical addition in aqueous media: Study of the solvent effect on radical addition reactions

A mixture of ethyl bromoacetate and 1-octene was treated with triethylborane in water at ambient temperature to provide ethyl 4-bromodecanoate in good yield. The bromine atom-transfer radical addition in benzene was not satisfactory. The addition proceeded smoothly in polar solvents such as DMF and DMSO, protic solvents such as 2,2,2-trifluoroethanol and 1,1,1,3,3,3-hexafluoro-2-propanol, and aqueous media. Ab initio calculations were conducted to reveal the origin of the solvent effect of water in the addition reaction. The polar effect of solvents, which is judged by the dielectric constant, on the transition states in the bromine atom-transfer and radical addition steps is moderately important. Calculations show that a polar solvent tends to lower the relative energies of the transition states. The coordination of a carbonyl group to a proton in a protic solvent, like a Lewis acid, would also increase the efficiency of the propagation.