Dioxomolybdenum(VI) complexes including MoO2(dipic)(HMPA) 2a and MoO2(dedtc)2 2b (dipic = 2,6-pyridinedicarboxylate; HMPA = hexamethylphosphoramide; dedtc = N,N-diethyl dithiocarbamate) catalyse the allylic amination of alkenes by phenyl hydroxylamine; the reactions are characterized by a high degree of regioselectivity resulting from double bond migration.