Selective Solvent-Free and Additive-Free Oxidation of Primary Benzylic C–H Bonds with O2 Catalyzed by the Combination of Metalloporphyrin with N-Hydroxyphthalimide

A protocol for solvent-free and additive-free oxidation of primary benzylic C–H bonds with O 2 was presented through adjusting the combination of metalloporphyrins and NHPI as binary catalysts to overcome the deficiencies encountered in current oxidation systems. The effects of reaction temperature, porphyrin structure, central metal, catalyst loading and O 2 pressure were investigated systematically. For the optimized combination of T(2-OCH 3 )PPCo and NHPI, all the primary benzylic C–H bonds could be functionalized efficiently and selectively at 120 °C and 1.0 MPa O 2 with aromatic acids as the primary products. The selectivity towards aromatic acids could reach up to 70–95% in the conversion of more than 30% for most of the substrates possessing primary benzylic C–H bonds in the metalloporphyrin loading of 0.012% (mol/mol). And the superior performance of T(2-OCH 3 )PPCo among the metalloporphyrins investigated was mainly attributed to its high efficiency in charge transfer and fewer positive charges around central metal Co (II) which favored the adduction of O 2 to cobalt (II) forming the high-valence metal-oxo complex followed by the production of phthalimide N-oxyl radical (PINO) and the initiation of the catalytic oxidation cycle. This work would provide not only an efficient protocol in utilization of hydrocarbons containing primary benzylic C–H bonds, but also a significant reference in the construction of more efficient C–H bonds oxidation systems. Graphic Abstract The solvent-free and additive-free oxidation of primary benzylic C–H bonds with O 2 was presented through adjusting the combination of metalloporphyrins and NHPI as binary catalysts, and the highest selectivity towards aromatic acid reached up to 95.1% with the conversion of 88.5% in the optimized combination of T(2-OCH 3 )PPCo and NHPI.