Photocatalytic Carboxylation of C−N Bonds in Cyclic Amines with CO₂ by Consecutive Visible‐Light‐Induced Electron Transfer

Abstract Visible‐light photocatalytic carboxylation with CO 2 is highly important. However, it still remains challenging for reluctant substrates with low reduction potentials. Herein, we report a novel photocatalytic carboxylation of C−N bonds in cyclic amines with CO 2 via consecutive photo‐induced electron transfer (ConPET). It is also the first photocatalytic reductive ring‐opening reaction of azetidines, pyrrolidines and piperidines. This strategy is practical to transform a variety of easily available cyclic amines to valuable β‐, γ‐, δ‐ and ϵ‐amino acids in moderate‐to‐excellent yields. Moreover, the method also features mild and transition‐metal‐free conditions, high selectivity, good functional‐group tolerance, facile scalability and product derivations. Mechanistic studies indicate that the ConPET might be the key to generating highly reactive photocatalysts, which enable the reductive activation of cyclic amines to generate carbon radicals and carbanions as the key intermediates.