Formation of TEMPO Adducts with Hydrogen Atom Transfer: An Alternative Pathway to Versatile Hydrofunctionalizations of Olefins

A two‐step process is developed to access a broad range of hydrofunctionalization of olefins, by combining a cobalt‐catalyzed formation of TEMPO adduct from olefins and a photocatalytic nucleophilic addition to generate a new C‐C, C‐N, C‐O, C‐F, and C‐Cl bond. Nucleophilic fluorination can be achieved with a short reaction time, showing its potential in PET applications. Combining the two steps, net hydrofunctionalization of olefins with a broad range has been achieved.