β -Functionalization of Saturated Aza-Heterocycles Enabled by Organic Photoredox Catalysis.

The direct β -functionalization of saturated aza-heterocycles has remained a synthetic challenge because of the remote and unactivated nature of β -C-H bonds in these motifs. Herein, we demonstrate the β -functionalization of saturated aza-heterocycles enabled by a two-step organic photoredox catalysis approach. Initially, a photoredox-catalyzed copper-mediated dehydrogenation of saturated aza-heterocycles produces ene-carbamates. This is followed by an anti-Markovnikov hydrofunctionalization of the ene-carbamates with a range of heteroatom-containing nucleophiles furnishing an array of C-C, C-O, and C-N aza-heterocycles at the β -position.