Enantioselective Organo‐Photocatalysis Mediated by Atropisomeric Thiourea Derivatives

Abstract Can photocatalysis be performed without electron or energy transfer? To address this, organo‐photocatalysts that are based on atropisomeric thioureas and display lower excited‐state energies than the reactive substrates have been developed. These photocatalysts were found to be efficient in promoting the [2+2] photocycloaddition of 4‐alkenyl‐substituted coumarins, which led to the corresponding products with high enantioselectivity (77–96 % ee ) at low catalyst loading (1–10 mol %). The photocatalytic cycle proceeds by energy sharing via the formation of both static and dynamic complexes (exciplex formation), which is aided by hydrogen bonding.