Modular Synthesis of Dehydroprolines by an Energy‐Transfer Enabled Cloke‐Wilson Rearrangement

Abstract A one‐pot photocatalytic method is reported for the generation of dehydroprolines, valuable precursors to 5‐aryl prolines. Imines, obtained via simple condensation of aminocyclopropane carboxylates (ACPC) with a broad range of aldehydes, were employed in this transformation without purification. We demonstrate this energy‐transfer (EnT) enabled Cloke‐Wilson‐type rearrangement affords both the rare 1,2‐dehydroprolines or the more thermodynamically favored 1,5‐isomers with up to >20 : 1 selectivity in both directions, using an identical catalytic system from the same starting material. Syntheses of intermediates of bioactive molecules in high yields and selectivity highlight this enabling transformation. Mechanistic studies support the proposed triplet‐triplet EnT mode of activation, distinct from the previously developed singlet excited states accessed via UV excitation.