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

N,O-Acetals derived from alpha,beta-unsaturated beta-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 (lambda = 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.

Automated summary

N,O-Acetals derived from alpha,beta-unsaturated beta-aryl substituted aldehydes and (1-aminocyclohexyl)methanol underwent a catalytic enantioselective [2 + 2] photocycloaddition to a variety of olefins with high yield and enantioselectivity under visible light irradiation using a chiral phosphoric acid as the catalyst. The formation of an iminium ion, the role of thioxanthone moieties, and the efficient enantioface differentiation were confirmed through NMR studies.