Solid-State Oxidation of Alcohols in Gold-Coated Milling Vessels via Direct Mechanocatalysis.

This paper presents a novel approach for the selective oxidation of alcohols to their corresponding aldehydes through direct mechanocatalysis, employing a gold-coated milling vessel as catalyst and air as the oxidation agent. By adjusting milling frequency, media, and duration, high catalytic efficiencies and selectivities are achieved. Remarkably, yields of up to 99 % are obtained for specific substrates, with a turnover number (TON) of 8200 and a turnover frequency (TOF) of 0.77 s-1, surpassing existing alternatives. Confirmation of the catalytic reaction indeed occurring on the milling tool surface was achieved through X-ray photoelectron spectroscopy (XPS).

Milling Medium-Free Suzuki Coupling by Direct Mechanocatalysis: From Mixer Mills to Resonant Acoustic Mixers.

Here we describe the development of a sustainable and cost-effective approach for catalytic cross-coupling reactions in mechanochemistry. It is found that the substrate's impact with the vessel wall alone is sufficient to initiate the reaction, thus indicating that milling balls function primarily as a mixing agent for direct mechanocatalytic Suzuki coupling. The absence of milling balls can be offset by adjusting the rheology using liquid-assisted grinding (LAG). The LAG sweet spot of 0.25 µL mg-1 is confirmed for both resonance acoustic mixers (RAMs) and ball-free mixer mills, and is higher than in the presence of milling balls. RAMs exhibit excellent performance in the Suzuki reaction, achieving yields of 90 % after 60 min and complete conversion after 90 min. The longevity of the milling vessel is significantly improved in a RAM, allowing for at least 20 reactions without deterioration.

The Sonogashira Coupling on Palladium Milling Balls-A new Reaction Pathway in Mechanochemistry.

Utilizing direct mechanocatalytical conditions, the Sonogashira coupling was successfully performed on the surface of milling tools by using pure Pd and Pd coated steel balls. The optimization of co-catalyst forming additives led to a protocol, which generates quantitative yields under aerobic conditions for various substrates within as little as 90 minutes. Using state-of-the-art spectroscopic, diffractive, as well as in situ methods lead to the identification of a previously unknown and highly reactive complex of the co-catalyst copper. This new complex differs substantially from the known complexes in liquid phase Sonogashira couplings, proving that reaction pathways in mechanochemistry may differ from those in established synthetic procedures.

From Inert to Catalytically Active Milling Media: Galvanostatic Coating for Direct Mechanocatalysis.

The inert milling balls, commonly utilized in mechanochemical reactions, were coated with a layer of Pd and utilized as catalyst in the direct mechanocatalytic Suzuki reaction. With high yields (>80 %), the milling balls can be recycled multiple times in the absence of any solvents, ligands, catalyst-molecules and -powders, while utilizing as little as 0.8 mg of Pd per coated milling ball. The coating sequence, the support material, and the layer thickness were examined towards archiving high catalyst retention, low abrasion and high conversion. The approach was transferred to the coating of milling vessels revealing the interplay between catalytically available surface area and the mechanical energy impact in direct mechanocatalysis.

The Direct Mechanocatalytic Suzuki-Miyaura Reaction of Small Organic Molecules.

The molecular Suzuki cross-coupling reaction was conducted mechanochemically, without solvents, ligands, or catalyst powders. Utilizing one catalytically active palladium milling ball, products could be formed in quantitative yield in as little as 30 min. In contrast to previous reports, the adjustment of milling parameters led to the complete elimination of abrasion from the catalyst ball, thus enabling the first reported systematic catalyst analysis. XPS, in situ XRD, and reference experiments provided evidence that the milling ball surface was the location of the catalysis, allowing a mechanism to be proposed. The versatility of the approach was demonstrated by extending the substrate scope to deactivated and even sterically hindered aryl iodides and bromides.

Mechanochemically Assisted Synthesis of Hexaazatriphenylenehexacarbonitrile.

1,4,5,8,9,11-hexaazatriphenylenehexacarbonitrile (HAT CN) was synthesized mechanochemically at room temperature. The coupling of hexaketocyclohexane and diaminomaleonitrile was conducted in 10 min by vibratory ball milling. The effects of milling parameters, acids, dehydrating agents, and liquid-assisted grinding were rationalized. With 67%, the yield of this mechanochemical approach exceeds that of state-of-the-art wet-chemical syntheses while being superior with respect to time-, resource-, and energy-efficiency as quantified via green metrics.