Metal‐Free C‐X Functionalization in Solid‐State via Photochemistry in Ball Mills

We report the first metal- and catalyst-free protocol for the facile cross-coupling of aryl halides towards C-B, C-P and C-S bonds under solid-state ball milling conditions via UV light irradiation. The reactions can be performed in the absence of bulk solvents at room temperature in a mixer mill, yielding up to 99 % and being tolerant towards various functionalized aryl halides (X=I or Br). Furthermore, we developed a novel photoreactor design increasing the light intensity. With this we could demonstrate that our protocol surpasses classical solvent based as well as purely mechanochemical approaches in terms of green metrics and energy efficiency.