Electrochemical Synthesis of C(sp)-Rich Heterocycles Mesolytic Cleavage of Anodically Generated Aromatic Radical Cations.

Herein we report an electrochemical deconstructive functionalization approach for the synthesis of C(sp)-rich heterocycles. The reaction proceeds the mesolytic cleavage of anodically generated aromatic radical cations and the trapping of formed carbocation intermediates with internal nucleophiles. The method has been demonstrated across various arylalcohol substrates to access a diverse range of C(sp)-rich heterocycles including tetrahydrofuran, tetrahydropyran, and pyrrolidine scaffolds (26 examples).

Amphiphilic Janus Particles for Aerobic Alcohol Oxidation in Oil Foams.

Amphiphilic Janus silica particles, tunable with oleophobic-oleophilic properties and low fluorine content (8 wt % F), exhibited prominent foamability for a variety of aromatic alcohols at low particle concentrations (<1 wt %) compared to randomly functionalized silica particles. When selectively loaded with Pd nanoparticles on the oleophilic hemisphere, the particles displayed more than a 2-fold increase in catalytic activity for the aerobic oxidation of benzyl alcohol compared to nonfoam bulk catalysis under ambient O pressure. The particles were conveniently recycled with high foamability and catalytic activity maintained for at least five consecutive runs.

Microstructured gas-liquid-(solid) interfaces: A platform for sustainable synthesis of commodity chemicals.

Gas-liquid-solid catalytic reactions are widespread in nature and man-made technologies. Recently, the exceptional reactivity observed on (electro)sprayed microdroplets, in comparison to bulk gas-liquid systems, has attracted the attention of researchers. In this perspective, we compile possible strategies to engineer catalytically active gas-liquid-(solid) interfaces based on membrane contactors, microdroplets, micromarbles, microbubbles, and microfoams to produce commodity chemicals such as hydrogen peroxide, ammonia, and formic acid.

Metal-Free Selective Synthesis of α,β-Unsaturated Aldehydes from Alkenes and Formaldehyde Catalyzed by Dimethylamine.

α,β-Unsaturated aldehydes are important building blocks for the synthesis of a wide range of chemicals, including polymers. The synthesis of these molecules from cheap feedstocks such as alkenes remains a scientific challenge, mainly due to the low reactivity of alkenes. Here we report a selective and metal-free access to α,β-unsaturated aldehydes from alkenes with formaldehyde.

Ethanol Foams Stabilized by Isobutyl-Based POSS-Organosilica Dual-Particle Assemblies.

Nonaqueous foams in low-surface tension solvents (<25 mN·m) are highly desired for applications in fire extinguishers and detoxification gels. However, their formation is a Holy Grail of the chemical industry due to the need for stabilizers with low surface energy and high recyclability. Herein, we disclose a new strategy to generate abundant foams in ethanol and a variety of low-surface tension solvents relying on the interfacial coadsorption of two different particles.

Enhanced Biphasic Reactions in Amphiphilic Silica Mesopores.

In this study, we investigated the effect of the pore volume and mesopore size of surface-active catalytic organosilicas on the genesis of particle-stabilized (Pickering) emulsions for the dodecanal/ethylene glycol system and their reactivity for the acid-catalyzed biphasic acetalization reaction. To this aim, we functionalized a series of fumed silica superparticles (size 100-300 nm) displaying an average mesopore size in the range of 11-14 nm and variable mesopore volume, with a similar surface density of octyl and propylsulfonic acid groups. The modified silica superparticles were characterized in detail using different techniques, including acid-base titration, thermogravimetric analysis, TEM, and dynamic light scattering.

Influence of Pore Size in Benzoin Condensation of Furfural Using Heterogenized Benzimidazole Organocatalysts.

A designed N-heterocyclic carbene (NHC) catalyst was covalently anchored on a range of mesoporous and hierarchical supports, to study the influence of pore size in the benzoin condensation of furfural. The structural and spectroscopic characteristics of the anchored catalysts were investigated, also with the help of molecular dynamics simulations, in order to rationalize the degree of stability and recyclability of the heterogenized organocatalysts. Quantitative yields (99 %) and complete recyclability were maintained after several cycles, vindicating the design rationale.

Oil foams stabilized by POSS/organosilica particle assemblies: application for aerobic oxidation of aromatic alcohols.

A novel amphiphilic polyhedral oligomeric silsesquioxane (POSS) with surfactant-like behavior was synthesized. By combining this new POSS, used as a frother, with surface-active catalytic organosilica particles, used as a stabilizer, we designed a dual particle system able to generate foams in pure organic solvents. Tunable foamability and foam stability were achieved in a variety of organic solvents by simply adjusting the POSS concentration.

Organic foams stabilized by Biphenyl-bridged organosilica particles.

Hypothesis: Can surface-active particles be designed à la carte just by incorporating functional groups mimicking the structure of the solvent and gas? This is based on the idea that, to achieve good foamability, the particle wettability needs to be finely tuned to adjust the liquid-particle and gas-particle surface tensions. In practice, could particles containing phenyl rings and alkyl chains assemble at the air-liquid interface and stabilize foams based on aromatic solvents?

Experiments: A library of organosilica particles was prepared by sol-gel synthesis using aromatic organosilane precursors. The particles were characterized by TGA, FTIR and C/Si MAS NMR.

Pickering Interfacial Catalysis for Aerobic Alcohol Oxidation in Oil Foams.

Oil foams stabilized by surface-active catalytic particles bearing fluorinated chains and Pd nanoparticles allowed fast and efficient aerobic oxidation of a variety of aromatic and aliphatic alcohols compared to bulk catalytic systems at ambient O pressure. High foam stability was achieved at low particle concentration (<1 wt %) provided that the contact angle locates in the range 41°-73°. The catalytic performance was strongly affected by the foaming properties, with 7-10 times activity increase in pure O compared to nonfoam systems.

Selective Acid-Catalyzed Hydroarylation of Nonactivated Alkenes with Aniline Assisted by Hexafluoroisopropanol.

The catalytic hydroarylation of nonactivated alkenes with aniline is a reaction of high interest, aiming at providing C-functionalized aniline derivatives that are important precursors for the fabrication of polyurethanes. However, this reaction remains a longstanding goal of catalysis, as it requires one to simultaneously address two important goals: (1) the very low reactivity of nonactivated alkenes and (2) control of the hydroarylation/hydroamination selectivity. As a result, the hydroarylation of aniline is mostly restricted to activated alkenes (i.

Multiphase Microreactors Based on Liquid-Liquid and Gas-Liquid Dispersions Stabilized by Colloidal Catalytic Particles.

Pickering emulsions, foams, bubbles, and marbles are dispersions of two immiscible liquids or of a liquid and a gas stabilized by surface-active colloidal particles. These systems can be used for engineering liquid-liquid-solid and gas-liquid-solid microreactors for multiphase reactions. They constitute original platforms for reengineering multiphase reactors towards a higher degree of sustainability.

Identification of active catalysts for the acceptorless dehydrogenation of alcohols to carbonyls.

Acceptorless dehydrogenation into carbonyls and molecular hydrogen is an attractive strategy to valorize (biobased) alcohols. Using 2-octanol dehydrogenation as benchmark reaction in a continuous reactor, a library of metal-supported catalysts is tested to validate the predictive level of catalytic activity for combined DFT and micro-kinetic modeling. Based on a series of transition metals, scaling relations are determined as a function of two descriptors, i.

Direct Catalytic Conversion of Furfural to Furan-derived Amines in the Presence of Ru-based Catalyst.

The production of amine intermediates from biomass is capturing increasing attention. Herein, a simple and efficient preparation of l furan-derived amines was developed [e.g.

Reductive Amination of Furanic Aldehydes in Aqueous Solution over Versatile Ni AlO Catalysts.

We disclose in this study a NiAlO catalyst prepared by coprecipitation for the reductive amination of biomass-derived aldehydes and ketones in aqueous ammonia under mild reaction conditions. The catalyst exhibited 99% yield toward 5-aminomethyl-2-furylmethanol in the reaction of 5-hydroxymethyl furfural with ammonia at 100 °C for 6 h under 1 bar H. The catalyst was further extended to the reductive amination of a library of aromatic and aliphatic aldehydes and ketones with a yield in the range 81-90% at optimized reaction conditions.

Colloidal tectonics for tandem synergistic Pickering interfacial catalysis: oxidative cleavage of cyclohexene oxide into adipic acid.

Supramolecular preorganization and interfacial recognition can provide useful architectures for colloidal building. To this aim, a novel approach, based on colloidal tectonics involving two surface-active particles containing both recognition and catalytic sites, has been developed for controlling the formation and the properties of Pickering emulsions. This was illustrated by the combination of dodecyltrimethylammonium phosphotungstate nanoparticles, [C][PWO], and silica particles functionalized with alkyl and sulfonic acid groups, [C /SOH]@SiO.

Nanomixing Effects in Glycerol/Dodecanol Pickering Emulsions for Interfacial Catalysis.

Pickering emulsions offer a promising platform for conducting interfacial reactions between immiscible reagents. Despite the significant progress in the engineering of amphiphilic catalysts for such reactions, the mechanism behind their enhanced activity is still poorly understood. Herein, using the glycerol/dodecanol system as a case study, we conducted a combined meso- and microscale study of Pickering emulsions stabilized by amphiphilic silica nanoparticles bearing acid centers by marrying dissipative particle dynamics simulations with emulsification experiments.

Direct Amination of Alcohols Catalyzed by Aluminum Triflate: An Experimental and Computational Study.

Among the best-performing homogeneous catalysts for the direct amination of activated secondary alcohols with electron-poor amine derivatives, metal triflates, such as aluminum triflate, Al(OTf) , stand out. Herein we report the extension of this reaction to electron-rich amines and activated primary alcohols. We provide detailed insight into the structure and reactivity of the catalyst under working conditions in both nitromethane and toluene solvent, through experiment (cyclic voltammetry, conductimetry, NMR spectroscopy), and density functional theory (DFT) simulations.

Selective Electrogenerative Oxidation of 5-Hydroxymethylfurfural to 2,5-Furandialdehyde.

2,5-furandialdehyde (DFF) was synthesized by electrogenerative oxidation of 5-hydroxymethylfurfural (HMF) over a PtRu catalyst with 89 % selectivity at 50 °C after 17 h. This approach opens an avenue for a selective, energy-efficient and green oxidation of biomass-derived platform alcohols to added-value chemicals.

Aquivion Perfluorosulfonic Superacid as an Efficient Pickering Interfacial Catalyst for the Hydrolysis of Triglycerides.

Rational design of the surface properties of heterogeneous catalysts can boost the interfacial activity in biphasic reactions through the generation of Pickering emulsions. This concept, termed Pickering interfacial catalysis (PIC), has shown promising credentials in acid-catalyzed transesterification, ester hydrolysis, acetalization, etherification, and alkylation reactions. PIC has now been applied to the efficient, solvent-free hydrolysis of the triglyceride glyceryl trilaurate to lauric acid, catalyzed by Aquivion perfluorosulfonic superacid at mild conditions (100 °C and ambient pressure).

Dynamics of Pickering Emulsions in the Presence of an Interfacial Reaction: A Simulation Study.

Pickering emulsions combining surface-active and catalytic properties offer a promising platform for conducting interfacial reactions between immiscible reagents. Despite the significant progress in the design of Pickering interfacial catalysts for a broad panel of reactions, the dynamics of Pickering emulsions under reaction conditions is still poorly understood. Herein, using benzene hydroxylation with aqueous HO as a model system, we explored the dynamics of benzene/water Pickering emulsions during reaction by dissipative particle dynamics.

Pickering interfacial catalysis for biphasic systems: from emulsion design to green reactions.

Pickering emulsions are surfactant-free dispersions of two immiscible fluids that are kinetically stabilized by colloidal particles. For ecological reasons, these systems have undergone a resurgence of interest to mitigate the use of synthetic surfactants and solvents. Moreover, the use of colloidal particles as stabilizers provides emulsions with original properties compared to surfactant-stabilized emulsions, microemulsions, and micellar systems.

Intrinsic flexibility of the zeolitic imidazolate framework ZIF-7 unveiled by CO₂ adsorption and Hg intrusion.

ZIF-7, built as an assembly of Zn(II) centers and benzimidazolate ligands, shows prominent S-shaped isotherms upon CO2 adsorption that can be attributed to sorbate-induced gate-opening phenomena involving a narrow-to-large pore phase transition. This peculiar sorption pattern can be captured via the formulation of thermodynamic isotherms, providing a direct enthalpic and entropic view of the gate-opening process. Relying on such an approach, an energy barrier with preferential enthalpic nature for CO2 adsorption/desorption in the gate-opening region could be unveiled.