Efficient, recoverable, copper-catalyzed aerobic oxidation of alcohols under FBS and thermomorphic mode

A series of fluorinated bipyridine derivatives, (4,4′-bis(RfCH2OCH2)-2,2′-bpy) {Rf = n-C8F17 (1a), n-C9F19 (1b), n-C10F21 (1c), n-C11F23 (1d)} have been successfully synthesized using 4,4′-bis(bromomethylene)-2,2′-bpy and fluorinated alkoxides. Bpy 1a-d have been characterized by multi-nuclei (1H, 19F, and 13C) NMR, GC/MS and FTIR. The Cu complexes 2a-d could be generated in situ by stirring ligands 1a-d with CuBr·Me2S at room temperature, respectively. The 3-component systems 3c-d, CuBr·Me2S/Bpy (1c-d)/2,2,6,6-Tetramethylpiperidine 1-oxyl (TEMPO), were successfully used to the aerobic oxidation of alcohols under the fluorous biphasic system (FBS). The resulting products from FBS could be easily recovered by two phase separation with high yields up to 8 runs (>90%). In order to avoid using the expensive fluorous solvents, systems 3a-d, CuBr·Me2S/Bpy (1a-d)/TEMPO, were also successfully shown to catalyze the aerobic alcohol oxidation under the thermomorphic condition (in C6H5Cl), and the yields of oxidation of 4-nitrobenzyl alcohol were close to 100% even after 8 runs. In particular, 3a was most effective under the thermomorphic mode in the chemoselectivity of aerobic oxidation of aliphatic primary alcohols to aldehydes without any overoxidized acids.

Graphical abstractThe 3-component systems 3c-d, CuBr·Me2S/Bpy (1c-d)/2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO), were successfully used to the aerobic oxidation of alcohols with high yields (up to 8 runs) under the fluorous biphasic system (FBS). In order to avoid using the expensive fluorous solvents, the systems 3a-d were also successfully shown to catalyze the aerobic alcohol oxidation under the thermomorphic mode. In particular, 3a was most effective under the thermomorphic mode in the chemoselectivity of aerobic oxidation of aliphatic primary alcohols to aldehydes without any over-oxidized acids.Download full-size image