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.
Highlights
A huge variety of compounds containing the carbonyl functional group is available from natural and commercial sources
Important insights the century, research has in on two ethers particular sets of oxime-derived compounds: (a) carbonyl and details of some surprising outcomes are described with particular emphasis on mechanistic and oxime derivatives and (b) O-aryl oxime ethers R R C=NOAr
Energy transfer between the MAP excited state and the iminyl portion of the oxime derivative was probably promoted by π–π-stacking of their aryl units
Summary
A huge variety of compounds containing the carbonyl functional group is available from natural and commercial sources. The N–O bonds in these compounds are usually comparatively weak; ~50 kcalmol in oximes [5] and only 33–37 kcalmol in O-phenyl oxime ethers [6] Homolytic scission of these N–O bonds can be accomplished either by photochemical or by thermal means yielding for each type an N-centred radical accompanied by one equivalent of its O-centred counterpart. Important insights the century, research has in on two ethers particular sets of oxime-derived compounds:. (a) carbonyl and details of some surprising outcomes are described with particular emphasis on mechanistic and oxime derivatives and (b) O-aryl oxime ethers R R C=NOAr. Recent advances, important insights computational aspects. Details of some surprising outcomes are described with particular emphasis on mechanistic and computational aspects
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