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Molecules 2016, 21(1), 63; doi:10.3390/molecules21010063

Functionalised Oximes: Emergent Precursors for Carbon-, Nitrogen- and Oxygen-Centred Radicals

EaStCHEM School of Chemistry, University of St. Andrews, St. Andrews, Fife KY16 9ST, UK
Academic Editor: Roman Dembinski
Received: 11 December 2015 / Revised: 29 December 2015 / Accepted: 30 December 2015 / Published: 7 January 2016
(This article belongs to the Special Issue 20th Anniversary of Molecules—Recent Advances in Organic Chemistry)

Abstract

Oxime derivatives are easily made, are non-hazardous and have long shelf lives. They contain weak N–O bonds that undergo homolytic scission, on appropriate thermal or photochemical stimulus, to initially release a pair of N- and O-centred radicals. This article reviews the use of these precursors for studying the structures, reactions and kinetics of the released radicals. Two classes have been exploited for radical generation; one comprises carbonyl oximes, principally oxime esters and amides, and the second comprises oxime ethers. Both classes release an iminyl radical together with an equal amount of a second oxygen-centred radical. The O-centred radicals derived from carbonyl oximes decarboxylate giving access to a variety of carbon-centred and nitrogen-centred species. Methods developed for homolytically dissociating the oxime derivatives include UV irradiation, conventional thermal and microwave heating. Photoredox catalytic methods succeed well with specially functionalised oximes and this aspect is also reviewed. Attention is also drawn to the key contributions made by EPR spectroscopy, aided by DFT computations, in elucidating the structures and dynamics of the transient intermediates. View Full-Text
Keywords: oxime esters; oxime ethers; free radicals; organic synthesis; photochemical reactions; EPR spectroscopy; photoredox catalysis; N-heterocycles oxime esters; oxime ethers; free radicals; organic synthesis; photochemical reactions; EPR spectroscopy; photoredox catalysis; N-heterocycles
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This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. (CC BY 4.0).

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Walton, J.C. Functionalised Oximes: Emergent Precursors for Carbon-, Nitrogen- and Oxygen-Centred Radicals. Molecules 2016, 21, 63.

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