Considering the synthetic value of introducing active alcoholic hydroxyl group, developing C–H functionalization of alcohols is of significance. Herein, we present a photochemical method that under visible light irradiation, selectfluor can effectively promote the oxidative cross-coupling between alcohols and heteroarenes without the external photocatalysis, achieving the selective α sp3 C–H arylation of alcohol, even in the presence of ether. The N-F activation of selectfluor under blue LEDs irradiation is evidenced by electron paramagnetic resonance (EPR) study, which is the key process for the oxidative activation of α sp3 C–H alcohols. The observed reactivity may have significant implications for chemical transformations.

Considering the synthetic value of phosphonates, developing powerful catalytic methods for the phosphonylation of C­(sp2)–H bonds is important. Herein, we achieve a visible-light-induced external oxidant-free oxidative phosphonylation of C­(sp2)–H bonds via the combination of photocatalysis and proton-reduction catalysis. Mechanistic studies indicate that the visible-light-induced electron-rich arene radical cation is the key reactive intermediate. The synthetic application of this approach is demonstrated in the late-stage functionalization of pharmaceutical molecules. This study may have significant implications for the functionalization of C­(sp2)–H bonds, especially for those that are sensitive to oxidative conditions.

An external oxidant-free synthesis of α-aminophosphonates by synergistically combining photocatalysis and proton-reduction catalysis is developed herein. The gram-scale experiment demonstrates the potential utility of this protocol. This study may have important implications for the functionalization of oxidant-sensitive C(sp)-H bonds.

Considering the ubiquitous C­(sp3)–H and the important value of alkylated heteroarenes, developing a universal method for C­(sp3)–H arylation with heteroarenes is significant. Herein, we proposed a method where Selectfluor can promote the oxidative C­(sp3)–H arylation with heteroarenes without external photocatalysis under visible-light irradiation. By EPR study, the N–F activation of Selectfluor by blue LED irradiation can generate the N radical cation, which is the key step for this conversion.