4.8 Review

Chiral Photocatalyst Structures in Asymmetric Photochemical Synthesis

Journal

CHEMICAL REVIEWS
Volume 122, Issue 2, Pages 1654-1716

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/acs.chemrev.1c00467

Keywords

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Funding

  1. NSF [CHE-1954262]
  2. NIH [GM095666, GM127545]
  3. NSF Graduate Research Fellowship Program [DGE-1747503]
  4. NIH Kirschstein-NRSA Postdoctoral Fellowship [F32GM134611]

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Asymmetric photocatalysis is a major research topic in contemporary synthetic organic chemistry. However, the discovery of general strategies for highly enantioselective photochemical reactions has been a recent development, leading to a somewhat limited variety of stereocontrolled photoreactions. This review summarizes the chiral catalyst structures that have been studied for solution-phase asymmetric photochemistry, providing insight into the logic required for highly effective stereocontrolled photocatalysis.
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.

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