Alkanes in Minisci-Type Reaction under Photocatalytic Conditions with Hydrogen Evolution

We report herein a protocol for the selective activation of C(sp3)–H bonds based on the interplay of two readily available organic catalysts and their successful implementation in cross-coupling azaarenes with alkanes. This Minisci-like reaction is promoted by visible light at room temperature and is free from chemical oxidants, metals, and chlorinated solvents. A wide range of substrates are compatible, including some bioactive molecules. Mechanistic studies support a dual catalytic cycle with H2 evolution.