3-Substituted quinoxalin-2(1H)-ones and various aryl-substituted or tethered olefins underwent an enantioselective, inter- or intramolecular aza Paternò-Büchi reaction upon irradiation at λ=420 nm in the presence of a chiral sensitizer (10 mol %). For the intermolecular reaction with 1-arylethenes as olefin components, the scope of the reaction was studied (14 examples, 50-99 % yield, 86-98 % ee). The absolute and relative configuration of the products were elucidated by single-crystal X-ray crystallography. The reaction is suggested to occur by triplet energy transfer in a hydrogen-bonded 1:1 complex between the imine substrate and the catalyst. The intramolecular cycloaddition, consecutive reactions of the product azetidines, and an alternative reaction mode of quinoxalinones were investigated in preliminary experiments.
Keywords: cycloaddition; heterocycles; hydrogen bonds; photochemistry; sensitizers.
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