Vinylcyclopropane [3+2] Cycloaddition with Acetylenic Sulfones Based on Visible Light Photocatalysis

The first intermolecular visible light [3+2] cycloaddition reaction performed on a meta photocycloadduct employing acetylenic sulfones is described. The developed methodology exploits the advantages of combining UV and visible‐light in a two‐step sequence that provides a photogenerated cyclopropane which, through a strain‐release process, generates a new cyclopentane ring while significantly increasing the molecular complexity. Mechanistic studies and DFT calculations indicate an energy transfer pathway for the visible light‐driven reaction step. This strategy could be extended to simpler vinylcyclopropanes.