Photocatalytic strategies for the valorization of feedstock chemicals in batch and flow

This PhD thesis presents the development of novel synthetic methodologies for the functionalization of feedstock chemicals under mild conditions, employing both batch and flow photochemical processes. Emphasizing the transformative role of radical chemistry, the work explores unique reactivity patterns that expand the synthetic toolbox available for organic chemists. A key achievement presented in this thesis is the photocatalytic conversion of abundant liquid and gaseous alkanes into value-added building blocks, enabled by the synergistic integration of photocatalysis with transition metal catalysis. The use of flow reactors is underscored for their critical role in facilitating fast, efficient, and safe handling of gaseous reagents under photochemical conditions. Furthermore, innovative metal-free photocatalytic approaches employing sulfonylhydrazones as radical acceptors have been developed to form C(sp³)−C(sp³) bonds. Using this new reactivity paradigm, a redesigned homologation of carboxylic acids highlights the potential of single-electron logic to address long-standing challenges in organic synthesis. Finally, a platform for synthesizing densely functionalized α-branched secondary amines via deoxygenative activation of the inert amide functionality using inexpensive reagents is presented. Overall, this thesis demonstrates the power of radical-based methodologies in advancing sustainable and efficient chemical transformations.