Evidence for Triplet Sensitization in the Visible‐Light‐Induced [2+2] Photocycloaddition of Eniminium Ions

Εniminium ions were prepared from the corresponding α,β-unsaturated carbonyl compounds (enones and enals), and were found to be promoted to their respective triplet states by energy transfer. The photoexcited intermediates underwent intra- or intermolecular [2+2] photocycloaddition in good yields (50-78 %) upon irradiation at λ=433 nm or λ=457 nm. Iridium or ruthenium complexes with a sufficiently high triplet energy were identified as efficient catalysts (2.5 mol % catalyst loading) for the reaction. The intermolecular [2+2] photocycloaddition of an eniminium ion derived from a chiral secondary amine proceeded with high enantioselectivity (88 % ee).