Reaction of [60]fullerene in toluene with diethyl methylmalonate (3a), diethyl ethylmalonate (3b), diethyl bromomalonate (3c), triethyl methanetricarboxylate (3d) and ethyl cyanoacetate (3e) in the presence of manganese(III) acetate dihydrate afforded benzyl-substituted unsymmetrical 1,4-adducts 4a-4e. Dibenzylated 1,4-adduct 5 and methanofullerene 6 were also obtained in the case of 3d and 3e, respectively. A possible reaction mechanism for the formation of the 1,4-adducts 4a-4e is proposed.