Alkane as Hydrogen Source: Pd/Photoredox Dual‐Catalysis Enables Mild Olefin Hydrogenation

ABSTRACT The development of safe and economical catalytic hydrogenation is a persistent challenge. The direct use of abundant alkanes as hydrogen donors under mild conditions is particularly desirable, yet conventional alkane dehydrogenation approaches for this purpose typically require harsh conditions (150°C–200°C) and tolerate a limited range of olefin substrates. Here, we report a cooperative palladium/photoredox catalytic system that enables the hydrogenation of unactivated olefins at room temperature using simple alkanes as the hydrogen source. This dual catalysis merges a photocatalyzed hydrogen atom transfer (HAT) from alkanes with a palladium‐catalyzed hydrogen transfer, achieving efficient olefin hydrogenation. Mechanistic studies support a radical‐mediated pathway and confirm alkanes as the hydrogen source. This operationally simple method exhibits broad substrate scope and functional group tolerance, allowing for the late‐stage modification of complex molecules under mild conditions. This work establishes a general strategy for alkane utilization as convenient and versatile hydrogen donors, offering a mild alternative to traditional hydrogenation methods that generally rely on H 2 gas.