Visible-light photoredox-catalyzed selective carboxylation of C(sp3)-F bonds with CO2

The dual role of CO2 as both an electron carrier and an electrophile is demonstrated here. Based on this concept, we realize a selective carboxylation of C(sp(3))-F bonds with CO2 to construct various alpha-fluorocarboxylic acids via visible-light photoredox catalysis. The fluorinated substrates undergo single-electron transfer reduction by electron-rich CO2 radical anions, which are generated from CO2 via sequential hydride-transfer reduction and hydrogen-atom transfer processes. This methodology could be applied in the late-stage functionalization of complex molecules.

Automated summary

This study demonstrates the dual role of CO2 as both an electron carrier and an electrophile, enabling selective carboxylation of C(sp(3))-F bonds to construct various alpha-fluorocarboxylic acids via visible-light photoredox catalysis. The fluorinated substrates undergo reduction by CO2 radical anions generated from sequential hydride-transfer reduction and hydrogen-atom transfer processes. This methodology shows promise for the late-stage functionalization of complex molecules.