Isolation and Synthesis of Novel Meroterpenoids from Rhodomyrtus tomentosa: Investigation of a Reactive Enetrione Intermediate

Rhodomyrtusials A–C, the first examples of triketone‐sesquiterpene meroterpenoids featuring a unique 6/5/5/9/4 fused pentacyclic ring system were isolated from Rhodomyrtus tomentosa, along with several biogenetically‐related dihydropyran isomers. Two bis‐furans and one dihydropyran isomer showed acetylcholinesterase (AChE) inhibitory activity. Structures of the isolates were unambiguously established by a combination of spectroscopic data, ECD analysis, and total synthesis. Bioinspired total syntheses of six isolates were achieved in six steps utilizing a reactive enetrione intermediate generated in situ from a readily available hydroxy‐endoperoxide precursor.     

Milling Down to Nanometers: A General Process for the Direct Dry Synthesis of Supported Metal Catalysts

Supported catalysts are among the most important classes of catalysts. They are typically prepared by wet‐chemical methods, such as impregnation or co‐precipitation. Here we disclose that dry ball milling of macroscopic metal powder in the presence of a support oxide leads in many cases to supported catalysts with particles in the nanometer size range. Various supports, including TiO₂, Al₂O₃, Fe₂O₃, and Co₃O₄, and different metals, such as Au, Pt, Ag, Cu, and Ni, were studied, and for each of the supports and the metals, highly dispersed nanoparticles on supports could be prepared. The supported catalysts were tested in CO oxidation, where they showed activities in the same range as conventionally prepared catalysts. The method thus provides a simple and cost‐effective alternative to the conventionally used impregnation methods.     

The Kirkendall Effect for Engineering Oxygen Vacancy of Hollow Co3O4 Nanoparticles toward High‐Performance Portable Zinc–Air Batteries

Structure and defect control are widely accepted effective strategies to manipulate the activity and stability of catalysts. On a freestanding hierarchically porous carbon microstructure, the tuning of oxygen vacancy in the embedded hollow cobaltosic oxide (Co₃O₄) nanoparticles is demonstrated through the regulation of nanoscale Kirkendall effect. Starting with the embedded cobalt nanoparticles, the concentration of oxygen‐vacancy defect can vary with the degree of Kirkendall oxidation, thus regulating the number of active sites and the catalytic performances. The optimized freestanding catalyst shows among the smallest reversible oxygen overpotential of 0.74 V for catalyzing oxygen reduction/evolution reactions in 0.1 m KOH. Moreover, the catalyst shows promise for substitution of noble metals to boost cathodic oxygen reactions in portable zinc–air batteries. This work provides a strategy to explore catalysts with controllable vacancy defects and desired nano‐/microstructures.     

Aqueous Electrochemical Reduction of Carbon Dioxide and Carbon Monoxide into Methanol with Cobalt Phthalocyanine

Conversion of CO₂ into valuable molecules is a field of intensive investigation with the aim of developing scalable technologies for making fuels using renewable energy sources. While electrochemical reduction into CO and formate are approaching industrial maturity, a current challenge is obtaining more reduced products like methanol. However, literature on the matter is scarce, and even more for the use of molecular catalysts. Here, we demonstrate that cobalt phthalocyanine, a well‐known catalyst for the electrochemical conversion of CO₂ to CO, can also catalyze the reaction from CO₂ or CO to methanol in aqueous electrolytes at ambient conditions of temperature and pressure. The studies identify formaldehyde as a key intermediate and an unexpected pH effect on selectivity. This paves the way for establishing a sequential process where CO₂ is first converted to CO which is subsequently used as a reactant to produce methanol. Under ideal conditions, the reaction shows a global Faradaic efficiency of 19.5 % and chemical selectivity of 7.5 %.     

Aerobic Toluene Oxidation Catalyzed by Subnano Metal Particles

Subnanocatalysts (SNCs) containing various noble metals (Cu, Ru, Rh, Pd, or Pt) with sizes of approximately 1 nm were synthesized using dendritic poly(phenylazomethine)s as a macromolecular template. These materials exhibit high catalytic performance during toluene oxidation without the use of harmful solvents or explosive oxidants, resulting in the formation of valuable organic products, including benzoic acid as the major product. In particular, Pt₁₉ SNC with a narrow particle size distribution exhibits extraordinary catalytic activity, with a turnover frequency of 3238 atom^?1 h^?1, which is 1700 times greater than that obtained by commercial Pt/C catalysts.     

Computational and Synthetic Investigation of Cationic Rearrangement in the Putative Biosynthesis of Justicane Triterpenoids

A biomimetic cationic structural rearrangement of the oleanolic acid framework is reported for the gram‐scale synthesis and structural reassignment of justicioside E aglycone. The mechanism of the putative biosynthetic rearrangement is investigated with kinetic, computational, and synthetic approaches. The precursor to rearrangement was accessed through two strategic advancements: (1) synthesis of a 1,3‐diketone via oxidation of a β‐silyl enone, and (2) diastereoselective 1,3‐diketone reduction to form a syn‐1,3‐diol using SmI₂ with PhSH as a key additive.