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Photoredox Catalysis: History
Please note this is an old version of this entry, which may differ significantly from the current revision.
Subjects: Chemistry, Organic
Contributor: Helena Kang

Photoredox catalysis is a catalytic mode in which a light-absorbing catalyst, upon excitation, engages in single-electron transfer with an organic substrate or a sacrificial redox partner, thereby generating radical or radical-ion intermediates under conditions that would not produce those intermediates thermally [1][2]. In radical photochemical reactions the concept is bounded by a closed photoredox cycle: the photocatalyst must be restored to its original oxidation state after the productive electron transfer. Essential features are a chromophore with a sufficiently long-lived excited state, a pair of excited-state redox potentials that match the substrate, and a subsequent radical transformation—addition, coupling, or fragmentation—of the photogenerated intermediate [1][3]. Catalysts include transition-metal polypyridyl complexes, especially iridium and ruthenium species, and organic dyes that operate by analogous electron-transfer cycles [1][2]. Dual catalytic systems merge the photoredox cycle with a second cycle, such as organocatalysis or nickel catalysis, so that the radical intermediate is intercepted in a controlled bond-forming step [4]. The concept is distinguished from direct photochemistry of the substrate, in which no catalytic chromophore mediates the electron transfer, and from energy-transfer photocatalysis, in which the excited catalyst transfers energy rather than an electron.

  • photoredox catalysis
  • single-electron transfer
  • photocatalyst
  • radical intermediate

Radical Photochemical Reactions • Organic Chemistry • Chemistry • Physical Sciences

References

  1. Christopher K. Prier; Danica A. Rankic; David W. C. MacMillan; Visible Light Photoredox Catalysis with Transition Metal Complexes: Applications in Organic Synthesis. Chem. Rev. 2013, 113, 5322-5363, 10.1021/cr300503r.
  2. Nathan A. Romero; David A. Nicewicz; Organic Photoredox Catalysis. Chem. Rev. 2016, 116, 10075-10166, 10.1021/acs.chemrev.6b00057.
  3. Jagan M. R. Narayanam; Corey R. J. Stephenson; Visible light photoredox catalysis: applications in organic synthesis. Chem. Soc. Rev. 2010, 40, 102-113, 10.1039/b913880n.
  4. David A. Nicewicz; David W. C. MacMillan; Merging Photoredox Catalysis with Organocatalysis: The Direct Asymmetric Alkylation of Aldehydes. Science 2008, 322, 77-80, 10.1126/science.1161976.
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