Photocatalytic Aerobic Phosphatation of Alkenes

Abstract A catalytic regime for the direct phosphatation of simple, non‐polarized alkenes has been devised that is based on using ordinary, non‐activated phosphoric acid diesters as the phosphate source and O 2 as the terminal oxidant. The title method enables the direct and highly economic construction of a diverse range of allylic phosphate esters. From a conceptual viewpoint, the aerobic phosphatation is entirely complementary to traditional methods for phosphate ester formation, which predominantly rely on the use of prefunctionalized or preactivated reactants, such as alcohols and phosphoryl halides. The title transformation is enabled by the interplay of a photoredox and a selenium π‐acid catalyst and involves a sequence of single‐electron‐transfer processes.