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Radical Reaction: 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

A radical reaction is a chemical transformation in which an open-shell species bearing one or more unpaired electrons is an essential intermediate, chain carrier, or product-determining species. Radicals can be generated by homolysis, single-electron transfer, hydrogen-atom transfer, photolysis, thermolysis, or redox activation. Their characteristic elementary steps include addition to π bonds, atom transfer, fragmentation, rearrangement, substitution, combination, and disproportionation [1]. A chain radical reaction contains initiation, propagation, and termination, whereas a nonchain radical process can proceed through discrete photochemical or electrochemical generation and trapping of each radical. Within radical photochemistry, light creates the radical directly or through excited-state electron or energy transfer [2]. The defining criterion is mechanistic participation of an open-shell intermediate, not merely exposure to light or an oxidant. Radical reactions are distinguished from closed-shell ionic and concerted pericyclic reactions by their one-electron bond-making and bond-breaking steps.

  • radical intermediate
  • open-shell reaction
  • photochemical initiation
  • radical cascade

Radical Photochemical Reactions • Organic Chemistry • Chemistry • Physical Sciences

References

  1. Gareth J. Rowlands; Radicals in organic synthesis. Part 1. Tetrahedron 2009, 65, 8603-8655, 10.1016/j.tet.2009.07.001.
  2. Matthew S. Galliher; Bec J. Roldan; Corey R. J. Stephenson; Evolution towards green radical generation in total synthesis. Chem. Soc. Rev. 2021, 50, 10044-10057, 10.1039/d1cs00411e.
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