Hexafluoroisopropanol‐Promoted or Brønsted Acid‐Mediated Photochemical [2+2] Cycloadditions of Alkynes with Maleimides

Abstract Although the use of light stimulating organic transformations has been known for more than a century, there is an increasing research interest on expanding the established knowledge. While [2+2] cycloadditions are promoted photochemically, literature precedent on the reaction between alkynes and maleimides is limited and only a handful of examples exist, focusing mainly on N ‐aliphatic maleimides. Herein, the differences in reactivity between N ‐alkyl and N ‐aryl maleimides were identified, and the use of hexafluoroisopropanol (HFIP) or trifluoroacetic acid (TFA) as viable solutions was proposed in order to achieve high yields. In the case of N ‐alkyl maleimides, both HFIP‐mediated or TFA‐promoted reactions were established using LED 370 nm irradiation, without the use of an external photocatalyst. In the case of N ‐aryl maleimides, thioxanthone (THX) was employed as the energy transfer photocatalyst along with LED 427 nm irradiation and HFIP. Mechanistic studies were performed, supporting the pivotal role of HFIP or TFA, in acquiring good to high yields in both classes of maleimides.