The oxidative kinetic resolution of racemic secondary alcohols was efficiently catalyzed by a chiral Mn(III)-salen complex using sodium hypochlorite (NaClO) as an oxidant in the presence of 8 mol% N-bromosuccinimide (NBS) in a dichloromethylene-water mixture solvent at room temperature. Excellent ee's (up to 99 %) of chiral secondary alcohols were achieved in most cases.

A catalytic system consisting of N,N-dimethyl-(4-(2,2,6,6-tetramethyl-1-oxyl-4-piperidoxyl)butyl)dodecyl ammonium bromide (TEMPO-Q), CuI and 2,2 0 -bipyridine was established. This catalytic system (CuI/bpy/TEMPO-Q) showed high activity and good to excellent selectivity in the oxidative conversion of various alcohols to the corresponding nitriles with molecular oxygen as terminal oxidant and aqueous ammonia as nitrogen source under solvent-free conditions. Besides, the catalytic system also offers the advantages of simplified workup procedure. This protocol thus represents a greener pathway for the synthesis of nitriles from alcohols.Graphical Abstract TEMPO-Q, a compound with both a TEMPO and a quaternary ammonium moieties, in combination with copper iodide and 2,2 0 -bipyridine as a catalytic system performed well in the oxidation of alcohols to nitriles with molecular oxygen as terminal oxidant in aqueous ammonia under solvent-free conditions. The catalytic system not only offers the advantages of simplified workup procedure, but also has high activity and selectivity due to the phase transfer catalysis of TEMPO-Q