Enantioselective catalysis of the intermolecular [2+2] photocycloaddition between 2-pyridones and acetylenedicarboxylates

Abstract

Intermolecular [2+2] photocycloadditions represent the most versatile and widely applicable of photochemical reactions. For the first time, such intermolecular reactions have been carried out in a catalytic fashion using a chiral triplet sensitizer, with high enantioselectivity (up to 92% ee). The low catalyst loading (2.5-5 mol%) underlines the high efficiency of the process both in terms of reaction acceleration and differentiation of the enantiotopic faces of the substrate. The substrate is anchored to the chiral catalyst through noncovalent interactions (hydrogen bonds), thus providing a chiral environment in which the enantioselective photocycloaddition proceeds. The densely functionalized products present numerous possibilities for further synthetic transformations.

Keywords: cycloaddition; enantioselectivity; hydrogen bonds; organocatalysis; photochemistry; sensitizers.