Mechanism of oxidation of primary and secondary alcohols by oxopiperidinium salts

Golubev, Valery A; Borislavskii, V. N.; Aleksandrov, A. L.

doi:10.1007/bf00924380

Cited by 24 publications

(55 citation statements)

References 6 publications

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“…Data reproduced from Golubev et al 59 deuterium isotope studies establish that the rate-determining step of the oxidations is the breaking of the carbon-hydrogen bond (Eq. 9), possibly in the form of a hydride abstraction.…”

Section: Figurementioning

confidence: 95%

“…The most comprehensive study of the mechanisms of oxoammonium oxidations of simple alcohols involves oxidations in water and aqueous acetonitrile at various pH values. 59 Two prevailing mechanisms are postulated, one dominating under acidic conditions, and another dominating under basic conditions. They are distinguished in two ways.…”

Section: Mechanistic Considerationsmentioning

confidence: 99%

“…2. 59 Three rate regimes for the primary alcohol, ethanol, and the secondary alcohol, 2-propanol, can be distinguished. 59 At pH values below 0, the reaction is greatly retarded.…”

Section: Mechanistic Considerationsmentioning

confidence: 99%

“…59 Three rate regimes for the primary alcohol, ethanol, and the secondary alcohol, 2-propanol, can be distinguished. 59 At pH values below 0, the reaction is greatly retarded. Above pH 0, each alcohol displays a pH-independent regime, with the secondary alcohol oxidizing significantly faster than the primary alcohol.…”

Section: Mechanistic Considerationsmentioning

confidence: 99%

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Oxoammonium‐ and Nitroxide‐Catalyzed Oxidations of Alcohols

2009

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The discovery in 1959 of stable nitroxide‐based free radicals such as the prototypical 2,2,6,6‐tetramethylpiperidine‐1‐oxyl (TEMPO) led to their use as electron spin resonance (ESR) spin labels in chemistry, biomedicine, and materials science. These nitroxides are prepared by the oxidation of secondary amines that contain no hydrogen atoms on the alpha‐carbons. The unique redox properties of nitroxides enable their use as oxidants in organic synthesis. The varied preparation and uses of oxoammonium salts as stoichiometric oxidants for alcohols are one subject of this review. Oxoammonium ions as oxidants for alcohols have a number of advantages, for example, the method is heavy‐metal free and some of the reactions can be performed in water or aqueous mixtures. A few side reactions are associated with these oxidations. The most serious is the fast reaction of the oxoammonium ion with free amines The several ways these oxidation reactions can be carried out are discussed in detail. They are: Oxidations using stoichimetric quantities of preformed oxoammonium salts carried out in either acidic, neutral, or basic conditions; reactions in which stoichiometric quantities of oxoammonium salts are generated in situ by disproportionation of a nitroxide in the presence of a strong acid; nitroxide‐catalyzed oxidations using a secondary oxidant; efficient nitroxide‐catalyzed oxidations of primary alcohols to carboxylic acids; and oxidations of primary alcohols or hemiacetals that can lead to lactones.

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Section: Figurementioning

confidence: 95%

Section: Mechanistic Considerationsmentioning

confidence: 99%

“…2. 59 Three rate regimes for the primary alcohol, ethanol, and the secondary alcohol, 2-propanol, can be distinguished. 59 At pH values below 0, the reaction is greatly retarded.…”

Section: Mechanistic Considerationsmentioning

confidence: 99%

Section: Mechanistic Considerationsmentioning

confidence: 99%

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Oxoammonium‐ and Nitroxide‐Catalyzed Oxidations of Alcohols

2009

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“…Nichtsdestotrotz wollen wir an dieser Stelle kurz auf den Mechanismus der Oxidationen bei niedrigem pH eingehen, für den ein Hydridtransfer gemäß Schema 4 vorgeschlagen wurde. [33,34] (Anelli-Bedingungen). [39] HOCl-vermittelte Oxidationen verlaufen unter milden Bedingungen, wobei Bromidionen als Cokatalysatoren agieren.…”

Section: Synthese Von Nitroxidenunclassified

Nitroxide: Anwendungen in der Synthese und in der Polymerchemie

2011

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Nitroxide werden in der Synthese und in der Polymerchemie verwendet. In diesem Aufsatz werden zunächst Methoden zur Herstellung von Nitroxiden und deren physikalische Eigenschaften besprochen. Der folgende Abschnitt beschreibt die Verwendung von Nitroxiden als stöchiometrische und katalytische Oxidationsmittel in der organischen Synthese. Die Oxidation von Alkoholen und Carbanionen spielt dabei ebenso eine wichtige Rolle wie oxidative C‐C‐Bindungsknüpfungen. Anschließend widmet sich ein Abschnitt der Rolle von Nitroxiden als Abfangreagentien für C‐zentrierte Radikale in der Radikalchemie. Nitroxide, die sich von Alkoxyaminen ableiten, fungieren als nützliche Ausgangsmaterialien für C‐zentrierte Radikale, deren Einsatz in der Synthese und in der Polymerchemie beschrieben wird. Der letzte Abschnitt stellt die Grundlagen der Nitroxid‐vermittelten Polymerisation (NMP) vor und zeigt neuere Entwicklungen beim Design komplexer Polymerarchitekturen auf.

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Nitroxide‐Catalyzed Alcohol Oxidations in Organic Synthesis

Brückner

2010

Stable Radicals

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Mechanism of oxidation of primary and secondary alcohols by oxopiperidinium salts

Cited by 24 publications

References 6 publications

Oxoammonium‐ and Nitroxide‐Catalyzed Oxidations of Alcohols

Oxoammonium‐ and Nitroxide‐Catalyzed Oxidations of Alcohols

Nitroxide: Anwendungen in der Synthese und in der Polymerchemie

Nitroxide‐Catalyzed Alcohol Oxidations in Organic Synthesis

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