Palladium‐Catalyzed Allylic Oxidation of Monoterpenic Alkenes with Molecular Oxygen

Palladium/p‐benzoquinone‐catalyzed aerobic oxidation of biomass‐based feedstock substrates, that is, limonene and α‐terpineol, has been developed. The system promotes an efficient dioxygen‐coupled catalytic turnover in the absence of auxiliary redox‐active co‐catalysts. Important for flavor and pharmaceutical industries, monoterpenic allylic acetates have been obtained in good to excellent yields. The regioselectivity of the limonene oxidation can be controlled through the appropriate choice of ligands and reaction conditions, which enables the variation of organoleptic properties of the product mixtures. The catalytic system can be applied generally to the allylic oxidation of simple cycloalkenes with molecular oxygen, for example, cyclohexene gives the corresponding allylic acetate in a nearly quantitative yield.

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