Triplet Energy Transfer from Ruthenium Complexes to Chiral Eniminium Ions: Enantioselective Synthesis of Cyclobutanecarbaldehydes by [2+2] Photocycloaddition.

ABSTRACT: Chiral eniminium salts, prepared from α,β-unsaturated aldehydes and a chiral proline derived secondary amine, underwent, upon irradiation with visible light, a ruthenium-catalyzed (2.5 mol %) intermolecular [2+2] photocycloaddition to olefins, which after hydrolysis led to chiral cyclobutanecarbaldehydes (17 examples, 49-74 % yield), with high diastereo- and enantioselectivities. Ru(bpz)3 (PF6 )2 was utilized as the ruthenium catalyst and laser flash photolysis studies show that the catalyst operates exclusively by triplet-energy transfer (sensitization). A catalytic system was devised with a chiral secondary amine co-catalyst. In the catalytic reactions, Ru(bpy)3 (PF6 )2 was employed, and laser flash photolysis experiments suggest it undergoes both electron and energy transfer. However, e

SUBMITTER: Hormann FM 

PROVIDER: S-EPMC7318320 | biostudies-literature | 2020 Jun

REPOSITORIES: biostudies-literature