Enantioselective Lewis Acid Catalysis of Intramolecular Enone [2+2] Photocycloaddition Reactions

Abstract

[2+2] Asymmetrically Catalysts in thermal reactions operate by lowering energy barriers of bound substrates, and thereby increasing the proportion of reagents that can proceed to products at a given temperature. In photochemical reactions, light provides the energy to surmount the barrier. It is therefore challenging to alter selectivity through catalysis, because the catalyst may not be bound when a given reagent absorbs the light. Brimioulle and Bach (p. 840 ) surmounted this problem in the light-induced intramolecular [2+2] cycloaddition of enones by using a catalyst that shifted the absorption wavelength of the bound substrate. The light was thus predominantly absorbed by substrate-catalyst complexes, enabling asymmetric induction by the catalyst to provide enantiomerically enriched products.