2. Photogeneration of Carboncentered Radicals

  1. Angelo Albini and
  2. Maurizio Fagnoni

Published Online: 12 JUL 2013

DOI: 10.1002/9781118689202.ch02

Photochemically-Generated Intermediates In Synthesis

Photochemically-Generated Intermediates In Synthesis

How to Cite

Albini, A. and Fagnoni, M. (eds) (2013) Photogeneration of Carboncentered Radicals, in Photochemically-Generated Intermediates In Synthesis, John Wiley & Sons, Inc., Hoboken, New Jersey. doi: 10.1002/9781118689202.ch02

Editor Information

  1. PhotoGreen Lab, Department of Chemistry, University of Pavia, Pavia, Italy

Publication History

  1. Published Online: 12 JUL 2013
  2. Published Print: 23 AUG 2013

ISBN Information

Print ISBN: 9780470915349

Online ISBN: 9781118689202

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Keywords:

  • alkyl radicals;
  • aryl radicals;
  • carbon-centered radicals;
  • photogeneration;
  • vinyl radicals

Summary

Among reactive intermediates, the use of carbon-centered radicals radicals has become an increasingly important and attractive tool for organic practitioners. This chapter discusses the photogeneration of alkyl radicals, vinyl radicals, and aryl radicals. The generation of alkyl radicals by fragmentation has been largely documented, or at least there are a large number of reports where the photochemical dehalogenation of organic compounds is suggested to operate. The photochemical generation of vinyl radicals is actually restricted to the photohomolysis of vinyl halides. An intrinsic drawback of this approach is that with these compounds the heterolytic cleavage of the C—X bond to yield vinyl cations competes. Photoreduction to the corresponding dehalogenated derivatives may be synthetically useful. Substituted carbon-centered radicals such as a,a-dioxy and a-oxy radicals, a-thioalkyl radicals, a-amino- and a-amidoalkyl radicals, halomethyl radicals, a-keto, a-carboxyl, and a-carbamoylalkyl radical, acyl radicals, and carbamoyl radicals are discussed in the chapter.