N-substituted trans-3, 4-dihydroxypiperidines 1–12 were synthesized by trans-hydroxylation of two series of tetrafluoroborates or trifluoroacetates of C-and N-substituted 1, 2, 5, 6- tetrahydropyridines (THPs) 13–24 by treatment with trifluoroperacetic acid or free THP bases by treatment with performic acid. Under these conditions, the nitrogen atom is blocked, which prevents the formation of N oxides deactivating the double bond.