NEW ALKANE FUNCTIONALIZATION REACTIONS BASED ON GIF-TYPE CHEMISTRY IN THE PRESENCE OF ALKALI-METAL SALTS

Cycloalkanes are transformed into monosubstituted cycloalkyl derivatives (chloride, azide, cyanide, thiocyanate, dicycloalkyl disulfide, or nitroalkane) in mostly good efficiencies by treatment with tert-butyl hydroperoxide in pyridine/acetic acid containing Fe(NO3)3.9H2O, in the presence of alkali metal salts (LiCl, NaN3,[Et4N]CN, NaSCN, Na2S, or NaNO2, respectively). In comparison, ionic trapping with Cu(OAc)2 gave efficient trapping with chloride ion, very inefficient capture of thiocyanate, and a significant difference in reactivity towards azide ion.