Photochemical [2+4]‐Dimerization Reaction from the Excited State

Aryl‐maleimides undergo a novel [2+4]‐photodimerization instead of the expected [2+2]‐photodimerization under both direct irradiation with visible light and under sensitized energy transfer conditions. This new excited state reactivity in aryl‐maleimides is deciphered through photochemical, photophysical, and spectroscopic studies. The stereochemistry of the photodimer depends on the type of non‐bonding interactions prevalent during photodimerization which is in turn dictated by the substituents on the maleimide ring. More importantly, the stereochemistry of the photodimer formed is complementary to the product observed under thermal conditions. Novel divergent excited state reactivity of aryl‐maleimides undergoing an unexpected [2+4]‐photodimerization is presented with detailed mechanistic rationale. The stereochemistry of the photodimer formed is complementary to the product observed under thermal conditions and is dictated by the type of non‐bonding interactions prevalent in the photoexcited reactant.