The Over-Riding Role of Autocatalysis in Allylic Oxidation

Peter J. Miedziak, Samuel Pattisson, Jennifer K. Edwards, Brian Tarbit, Stuart H. Taylor, Graham J. Hutchings*

*Corresponding author for this work

    Research output: Contribution to journalArticlepeer-review

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    Abstract

    In this paper we aim to highlight the need to consider the possible role of autocatalysis in oxidation reactions when using molecular oxygen as the terminal oxidant. Oxygen in its ground state is a diradical, and depending on the reaction conditions, it can initiate oxidation through radical pathways through mechanisms which do not require the presence of a catalyst. Consequently, we contrast the oxidation of benzyl alcohol with oxidation of α-pinene. For benzyl alcohol oxidation the initial reaction is the oxidative dehydrogenation to form benzaldehyde, a non-radical process; but the subsequent over-oxidation to benzoic acid is a radical process. In this case the role of the autocatalysed reaction can be minimised. With α-pinene, the oxidation reaction is via radical pathways and now the autocatalysed reaction can be dominant and, indeed, can be the preferred pathway for the formation of high yields of the desired verbenone product. 

    Original languageEnglish
    Pages (from-to)1003-1008
    Number of pages6
    JournalCatalysis Letters
    Volume152
    Issue number4
    DOIs
    Publication statusPublished - 11 Jun 2021

    Keywords

    • Autocatalysis
    • Benzyl alcohol
    • Oxidation
    • α-pinene

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