We report herein a one-step synthesis of valuable enantioenriched piperidines and tetrahydroisoquinolines from readily available racemic 1,5-diols. Key to the success is the development of new iridacycle catalysts that enable efficient redox-neutral construction of two C-N bonds between diols and amines in an enantioconvergent fashion. Mechanistic studies identified an intriguing preferential oxidation of secondary versus primary alcohol in the diol substrate by the iridacycle catalyst, which set a challenging intermolecular amination of aryl-alkyl-substituted alcohol as the enantiodetermining step for this catalytic N-heterocycle synthesis. Application of this catalytic method to the preparation of important drugs and bioactive compounds is also demonstrated.