Mechanistic Insights into Aerobic C(sp 3 )–H Hydroxylation: A Catalytic Reaction or Not

The mechanism of aerobic C(sp³)-H hydroxylation to α-hydroxy ketone is investigated by multiple quantum chemical computations. An alkali-metal-assisted electron transfer (AET) is proposed to drive the triplet-to-singlet transition for C-O bond formation. The O-O bond cleavage is the key to catalytic conversion, which depends on different alkali metal bases and reductants.