A photochemical microfluidic reactor for photosensitized [2+2] cycloadditions

Here we report a microfluidic system for photochemical cycloadditions fabricated using silicon micro processing technologies. The system was optimized to yield residence times of just a few minutes for a range of photochemical [2+2]-cycloaddition reactions facilitated using high power UV-LEDs at 375 nm and triplet photosensitizers, which removed the need for the low wavelengths typically required for these types of transformations. Adducts using different excitable olefins with different linear-, carbocyclic- and heterocyclic coupling partners were explored to demonstrate the feasibility of performing photochemistry in microflow in an academic research environment. Finally, a reaction leading to a novel dihydrooxepin-2(3H)-one scaffold, and a mechanistic proposal for its formation are reported.