Selective Catalytic Oxidation of Benzyl Alcohol to Benzaldehyde With Alkyl Allyl Carbonates and Pd(II) Allyl‐Amidinate

ABSTRACT Group 9 and 10 amidinate complexes have been used as molecular precursors for surface organometallic chemistry (SOMC) and atomic layer deposition (ALD) because they readily react with OH functionalities, reversibly forming a metal oxygen bond. Here, we show that this reversible protonation step can be exploited to design a catalytic oxidation process of benzyl alcohol, where catalytic turnover is enabled by the addition of alkyl allyl carbonates in the presence of a catalytic amount of Pd(allyl)(DIA). Although overoxidation products are observed, we also present strategies to suppress their formation to obtain benzaldehyde in up to 95% yield. The presented work comprises a new strategy for the selective catalytic oxidation of alcohols to aldehydes, a fundamental reaction of organic chemistry.