Mechanometallaphotoredox catalysis: utilizing increased throughput mechanochemistry to develop solvent-minimized aryl amination and C(sp2)-C(sp3) cross-coupling reactions with increased tolerance to aerobic conditions

Photocatalysis as a tool used in organic synthesis has predominantly relied on the use of solvents, be it under homogeneous or heterogeneous conditions. In particular, metallaphotoredox catalysis reactions commonly use toxic organic solvents such as DMA and DMF. Herein, we demonstrate how mechanophotocatalysis, the synergistic union of mechanochemistry and photocatalysis, is compatible with this class of dual catalysis reactions involving both photocatalyst and nickel(II) cocatalysts. Using ball milling, these mechanistically complex reactions can be conducted in the absence of a bulk solvent and under air, affording high-yielding aryl aminations and C(sp2)-C(sp3) cross-couplings with alkyl carboxylic acids, alkyl trifluoroborate salts, and alkyl bromides. These advances are facilitated by the introduction of a novel reaction vessel design for conducting four mechanophotocatalysis reactions simultaneously. This work highlights the promise of solvent-minimized photocatalysis reactions, demonstrating that in these examples bulk solvent is redundant, thus significantly reducing this waste stream. Through time-resolved photoluminescence studies, we observed that the excited states of five different photocatalysts were quenched by oxygen more significantly in solution than in the solid state, providing evidence for the origin of the increased tolerance to aerobic conditions that these mechanophotocatalysis reactions experience.