Enantioselective [2 + 2] Photocycloaddition via Iminium Ions: Catalysis by a Sensitizing Chiral Brønsted Acid

Abstract

N,O-Acetals derived from α,β-unsaturated β-Aryl substituted aldehydes and (1-Aminocyclohexyl)methanol were found to undergo a catalytic enantioselective [2 + 2] photocycloaddition to a variety of olefins (19 examples, 54-96% yield, 84-98% ee). The reaction was performed by visible light irradiation (λ = 459 nm). A chiral phosphoric acid (10 mol %) with an (R)-1,1′-bi-2-naphthol (binol) backbone served as the catalyst. The acid displays two thioxanthone groups attached to position 3 and 3′ of the binol core via a meta-substituted phenyl linker. NMR studies confirmed the formation of an iminium ion which is attached to the acid counterion in a hydrogen-bond assisted ion pair. The catalytic activity of the acid rests on the presence of the thioxanthone moieties which enable a facile triplet energy transfer and an efficient enantioface differentiation.