The superiority of cuprous chloride to iodide in the selective aerobic oxidation of benzylic alcohols at ambient temperature

Cuprous halides, best described as (CuX) n (X = Cl − , Br − , and I − ) in their solid state, catalyse selective aerobic oxidation of alcohols with the assistance of both NMI ( N ‐methylimidazole) and TEMPO (2,2,6,6‐tetramethylpiperidine‐1‐oxyl), and the iodide generally demonstrates the highest activity, for example, in the oxidation of 1‐octanol at ambient temperature under 24 h' reaction. However, in the aerobic oxidation of benzylic alcohols, the chloride showed superiority to the iodide in that the aerobic oxidation was quantitatively completed within 3 h at ambient temperature whereas the iodide showed only about half the activity of the chloride analogue. By probing the system using electrochemistry, electric conductivity, and 1 H NMR titration, it was revealed that the surprising anomaly was due to the difference in the rate of forming active species, [Cu (NMI) 2 X(MeCN)], from the polymeric solid in a two‐stage process. Substrates expansion of 11 benzylic alcohols indicated that CuCl/NMI/TEMPO system demonstrated quantitative conversion of benzylic alcohols into corresponding aldehydes within 3 h and showed great tolerance to the substituents on the phenyl ring of the substrates. Furthermore, electron‐withdrawing substituent was beneficial to the oxidation and could offset the steric effect at orthro ‐substituent. Such a behaviour suggested that in the catalysis, increasing the acidity of the hydroxyl group (OH) of the substrates could ease the oxidation, which implied that the deprotonation via an internal pathway might be one of the rate‐determining steps. Our results also showed that the anion halide participated actively in the catalysis by coordinating to Cu(I) in the active species.