Alkyl radicals generated via an acridine photocatalyzed decarboxylation reaction of feedstock carboxylic acids engage with a range of cyclic imine-BF3 complexes to provide α-functionalized azacycles in an operationally simple process. A three-component variant of this transformation incorporating [1.1.1]propellane as an additional reaction partner enables the synthesis of valuable bicyclopentane (BCP)-containing azacycles. Reactions exhibit good functional group compatibility, enabling late-stage modification of complex bioactive molecules.