1996
DOI: 10.1021/jo961366q
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Radical versus “Oxenoid” Oxygen Insertion Mechanism in the Oxidation of Alkanes and Alcohols by Aromatic Peracids. New Synthetic Developments

Abstract: Evidences concerning a novel free-radical mechanism for the oxidation of alkanes by aromatic peracids are reported. The mechanism involves hydrogen abstraction from the OH group of peracids by an aroyloxyl radical; the acylperoxyl radical thus generated is responsible for the selective oxidation. The reaction is affected by the presence of oxygen and it is inhibited by TEMPO and by solvents forming hydrogen bonds with peracids. A more simple and effective synthetic procedure has been developed, on the basis of… Show more

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Cited by 77 publications
(71 citation statements)
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References 29 publications
(32 reference statements)
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“…(4)): (26) Nitroxyl radicals are generally electrophilic, but this polar character is considerably enhanced by the presence of two carbonyl groups (Eq. (27)): (27) The effect is similar to those observed with acylperoxyl, RC( O)OO • , and acyloxyl, RC( O)O • radicals compared to peroxyl, ROO • , and alkoxyl, RO • , radicals; the former are more electrophilic than the latter [25]. The phenomenon is more marked with PINO than with acylperoxyl and acyloxyl radicals because the nitrogen atom can stabilize a positive charge, as in Eq.…”
Section: Introductionsupporting
confidence: 64%
“…(4)): (26) Nitroxyl radicals are generally electrophilic, but this polar character is considerably enhanced by the presence of two carbonyl groups (Eq. (27)): (27) The effect is similar to those observed with acylperoxyl, RC( O)OO • , and acyloxyl, RC( O)O • radicals compared to peroxyl, ROO • , and alkoxyl, RO • , radicals; the former are more electrophilic than the latter [25]. The phenomenon is more marked with PINO than with acylperoxyl and acyloxyl radicals because the nitrogen atom can stabilize a positive charge, as in Eq.…”
Section: Introductionsupporting
confidence: 64%
“…Other types of reagents that play an important role in alkane chemistry are peroxo species like dioxiranes, [52] peracids, [53] as well as metal-oxo compounds. [54] The CÀH activations with peracids and dioxiranes are believed to occur through concerted insertions, [55] that is, they are mechanistically different from radical abstractions.…”
Section: Wwwchemeurjorgmentioning
confidence: 99%
“…(18) The effects are similar to those observed with acyl peroxyl, RC(ϭO)OO · , and acyloxyl, RC(ϭO)O · , radicals when compared to alkyl peroxyl, ROO · , and alkoxyl, RO · , radicals; the former are more electrophilic than the latter. [23] The phenomenon is more marked with PINO than with acylperoxyl and acyloxyl radicals because the nitrogen atom can stabilise a positive charge, as in Equation (18), better than carbon or oxygen atoms.…”
Section: Wwweurjocorgmentioning
confidence: 99%