Phase-vanishing halolactonization of neat substrates

Abstract

Phase-vanishing reactions are triphasic reactions which involve a reagent, a liquid perfluoroalkane as a phase screen and a substrate. The perfluoroalkane does not dissolve any of the reactants and is used to separate them. Halolactonization of neat substrates under phase-vanishing conditions avoids use of both solvents and basic reaction conditions. Both γ,δ-alkenoic acids as well as the corresponding methyl esters are suitable substrates for phase-vanishing halolactonizations. The reaction works well both on solid and liquid substrates and the products are obtained in good to excellent yields, particularly in the case of rigid bicyclic systems. Bromine (Br2) and iodine monochloride (ICl) are suitable electrophiles for bromolactonization and iodolactonization, respectively. Although in some cases iodine gave satisfactory yields of the corresponding iodolactone, it is generally inferior to iodine monochloride. © 2008 Windmon et al; licensee Beilstein-Institut.