Chiral Photocatalyst Structures in Asymmetric Photochemical Synthesis

Asymmetric catalysis is a major theme of research in contemporary synthetic organic chemistry. The discovery of general strategies for highly enantioselective photochemical reactions, however, has been a relatively recent development, and the variety of photoreactions that can be conducted in a stereocontrolled manner is consequently somewhat limited. Asymmetric photocatalysis is complicated by the short lifetimes and high reactivities characteristic of photogenerated reactive intermediates; the design of catalyst architectures that can provide effective enantiodifferentiating environments for these intermediates while minimizing the participation of uncontrolled racemic background processes has proven to be a key challenge for progress in this field. This review provides a summary of the chiral catalyst structures that have been studied for solution-phase asymmetric photochemistry, including chiral organic sensitizers, inorganic chromophores, and soluble macromolecules. While some of these photocatalysts are derived from privileged catalyst structures that are effective for both ground-state and photochemical transformations, others are structural designs unique to photocatalysis and offer insight into the logic required for highly effective stereocontrolled photocatalysis.