Alcohol oxidations are typically performed with stoichiometric reagents that generate heavy-metal waste and are usually run in chlorinated solvents. A water-soluble palladium(II) bathophenanthroline complex is a stable recyclable catalyst for the selective aerobic oxidation of a wide range of alcohols to aldehydes, ketones, and carboxylic acids in a biphasic water-alcohol system. The use of water as a solvent and air as the oxidant makes the reaction interesting from both an economic and environmental point of view.

https://science.sciencemag.org/content/sci/287/5458/1636.full.pdf

Green, catalytic oxidation of alcohols in water

Organic Carbonates as Solvents in Synthesis and Catalysis

Palladium- or nickel-catalyzed cross coupling. A new selective method for carbon-carbon bond formation

Treatment of a stoichiometric hydroxyapatite (HAP), Ca10(PO4)6(OH)2, with PdCl2(PhCN)2 gives a new type of palladium-grafted hydroxyapatite. Analysis by means of powder X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), energy-dispersive X-ray (EDX), IR, and Pd K-edge X-ray absorption fine structure (XAFS) proves that a monomeric PdCl2 species is chemisorbed on the HAP surface, which is readily transformed into Pd nanoclusters with a narrow size distribution in the presence of alcohol. Nanoclustered Pd0 species can effectively promote the alcohol oxidation under an atmospheric O2 pressure, giving a remarkably high turnover number (TON) of up to 236,000 with an excellent turnover frequency (TOF) of approximately 9800 h(-1) for a 250-mmol-scale oxidation of 1-phenylethanol under solvent-free conditions. In addition to advantages such as a simple workup procedure and the ability to recycle the catalyst, the present Pd catalyst does not require additives to complete the catalytic cycle. The diameters of the generated Pd nanoclusters can be controlled upon acting on the alcohol substrates used. Oxidation of alcohols is proposed to occur primarily on low-coordination sites within a regular arrangement of the Pd nanocluster by performing calculations on the palladium crystallites.

Hydroxyapatite-Supported Palladium Nanoclusters: A Highly Active Heterogeneous Catalyst for Selective Oxidation of Alcohols by Use of Molecular Oxygen

New developments in catalytic alcohol oxidations for fine chemicals synthesis

Hydrozirconation. III. Stereospecific and Regioselective Functionalization of Alkylacetylenes via Vinylzirconium(IV) Intermediates

PdCl2–NaOAc catalyses the homogeneous oxidation of secondary alcohols to ketones by O2 at room temperature.

Thomas F. Blackburn

Papers

Hydrozirconation. III. Stereospecific and Regioselective Functionalization of Alkylacetylenes via Vinylzirconium(IV) Intermediates

Homogeneous catalytic oxidation of secondary alcohols to ketones by molecular oxygen under mild conditions

Hydrozirconation. IV. Oxidation of alkylzirconium(IV) complexes to alcohols

Hydrozirconation part 3, stereospecific and regioselective functionalization of alkylacetylenes via vinylzirconium(iv) intermediates

Homogeneous catalytic oxidation of secondary alcohols to ketones by molecular oxygen under mild conditions