Photocycloaddition of 3-alkenyloxy-2-cycloalkenones: Enantioselective lewis acid catalysis and ring expansion

By application of substoichiometric amounts (50 mol %) of a chiral Lewis acid, the intramolecular [2+2] photocycloaddition of the title compounds was achieved with high enantioselectivity (up to 94 % ee). Upon cleavage of the cyclobutane ring the resulting tricyclic products underwent ring-expansion reactions under acidic conditions and formed anellated seven- or eight-membered-ring systems without racemization. The ring expansion could be combined with a diastereoselective reduction (triethylsilane) or allylation (allyltrimethylsilane) upon BF₃ catalysis (48-87 % yield). Ring-a-ring o'roses: An enantioselective, Lewis acid catalyzed [2+2] photocycloaddition (9 examples, 69-94 % yield, up to 94 % ee) leads to tricyclic products, in which the marked bond of the cyclobutane ring can be cleaved to form medium-sized rings as shown in the example above.