Radical-type addition of benzyl bromide to vinyl chloride: the kinetics and activation energy of the process

Ionic liquids in Barbier-Zaitsev reaction. Synthesis of 1-(perfluorophenyl)-2-phenylethanol in the presence of iron pentacarbonyl

“…Yet the addition of benzyl bromide to various functionally substituted compounds [1] is a promising route for the organic synthesis. These reactions are possible only at the use of metallocomplex initiators [2], for instance, the radical addition to the double C=C bond and the telomerization involving the benzyl bromide proceed under the action of the iron pentacarbonyl only in the presence of nucleophilic additive [3]. We have demonstrated that Fe(CO) 5 is an efficient promotor of the alkyl halides addition to the double bonds [1,3] C=C and C=O, and also of nitriles and esters of halogen-substituted acids to benzaldehydes and perfluorinated ketones by the type of reactions of Reformatsky [4] and Barbier-Zaitsev [5,6].…”

“…These reactions are possible only at the use of metallocomplex initiators [2], for instance, the radical addition to the double C=C bond and the telomerization involving the benzyl bromide proceed under the action of the iron pentacarbonyl only in the presence of nucleophilic additive [3]. We have demonstrated that Fe(CO) 5 is an efficient promotor of the alkyl halides addition to the double bonds [1,3] C=C and C=O, and also of nitriles and esters of halogen-substituted acids to benzaldehydes and perfluorinated ketones by the type of reactions of Reformatsky [4] and Barbier-Zaitsev [5,6]. However benzyl bromide is an exception from this series for its addition to aromatic aldehydes initiated by Fe(CO) 5 along the Barbier-Zaitsev reaction becomes possible only in the presence of nucleophilic additives (HMPA, DMF) [6], and in both cases alongside the addition product forms dibenzyl as a side product.…”