Mild Conditions Research Articles

Cs-Ba-Ru/La2O3-MgO Catalysts from Microdrop-Confined Pyrolysis for Superior NH3 Synthesis under Mild Conditions.

Support modification is an important way to improve the activity of the Ru/MgO-based NH3 synthesis catalyst. This work synthesized 24 composite MgO-based supports of MOx-MgO (M = La, Zn, etc.) via a microdrop-confined pyrolysis (MDCPy) method and then prepared the corresponding Cs-Ba-Ru/MOx-MgO catalysts using the impregnation method. Under the same NH3 synthesis conditions, the activity of the Cs-Ba-Ru/MOx-MgO catalysts composed of 17 elements such as Pr was significantly lower than that of Cs-Ba-Ru/MgO, while the activity of the Cs-Ba-Ru/MOx-MgO catalysts composed of four elements such as Nd was comparable to that of Cs-Ba-Ru/MgO, and the activity of the Cs-Ba-Ru/MOx-MgO catalysts composed of three elements such as La was significantly higher than that of Cs-Ba-Ru/MgO. Among them, it is clear that La2O3-MgO composite supports have the most significant effect on the improvement of NH3 synthesis performance. Through the optimization of the La/Mg ratio and loading of Ru, the optimal activities achieved ∼7 mol(NH3)/g(Ru)/h with corresponding Ru loading of 0.25-0.5 wt % under mild conditions as follows: H2/N2 ratio of 3:1, temperature of 400 °C, pressure of 3 MPa and a weight hourly space velocity (WHSV) of 96.0 L/gcat/h. In addition, the CsBa-Ru/La2O3-MgO catalyst showed good stability.

Electrochemical Giese Reaction of α-Trifluoromethylstyrenes with Disulfides: Efficient Access to β-Trifluoromethylated Thioethers.

An electrochemical Giese-type hydrothiolation of α-trifluoromethylstyrenes with disulfides is disclosed for the first time under metal-free and mild conditions. This approach provides a facile methodology for β-trifluoromethylated thioethers in moderate to good yields with high functional group tolerance starting from readily available substrates. Additionally, late-stage modification of drug molecules and gram-scale synthesis show practical advantages. The radical pathway of this reaction has been revealed by control experiments and cyclic voltammetry measurements.

Iodine/DMF-Mediated Regioselective Sulfenylation Using Arenediazonium Tosylates and Sodium Metabisulfite: An Easy Access to 3-Arylthioindoles.

A practical C3 sulfenylation of indoles has been accomplished using arenediazonium tosylates and sodium metabisulfite, with a key role of iodine/DMF combination in the reaction. The method involves scarce use of sodium metabisulfite as a divalent sulfur source and offers an array of structurally diverse 3-arylthioindoles in high yields under operationally simple transition-metal-free and mild conditions.

Direct Synthesis of Artificial Esterase through Molecular Imprinting Using a Substrate-Mimicking Acylthiourea Template.

Most reported artificial esterases hydrolyze only activated esters. We here report a one-pot synthesis of artificial esterases via molecular imprinting. An acylthiourea template hydrogen bonds with 4-vinylbenzoic acid and coordinates to a polymerizable zinc complex inside a cross-linkable surfactant micelle. Double cross-linking of the micelle yields a polymeric nanoparticle catalyst that mimics a metalloenzyme to activate a water molecule for nucleophilic attack on the bound ester. The catalyst hydrolyzes both activated and unactivated esters under mild conditions with selectivity.

Multifunctional Polymer Synthesis via Sequential Postpolymerization Modification Using a Single Aldehyde Repeat Unit: Allylation and Orthogonal Esterification and Thiol-ene Reaction.

Herein, we present a highly efficient method for synthesizing multifunctional polymers. This method involves the sequential postpolymerization modification (PPM) of a highly reactive aldehyde polymer. We introduce an allylic alcohol functionality into the polymer backbone via Barbier-type allylation, a process facilitated by easy-to-handle indium(0) powder. This step enables the formation of orthogonal pendants, secondary alcohol, and terminal alkene, which can be further functionalized through esterification and thiol-ene click reactions. All of these processes are carried out under mild conditions, ensuring high efficiency and a wide range of functional groups. Our study underscores PPM's operational simplicity and versatility in developing advanced polymer materials and expanding the scope of multifunctional polymer design.

A unified structure-preserving parametric finite element method for anisotropic surface diffusion

We propose and analyze a unified structure-preserving parametric finite element method (SP-PFEM) for the anisotropic surface diffusion of curves in two dimensions ( d = 2 ) (d=2) and surfaces in three dimensions ( d = 3 ) (d=3) with an arbitrary anisotropic surface energy density γ ( n ) \gamma (\boldsymbol {n}) , where n ∈ S d − 1 \boldsymbol {n}\in \mathbb {S}^{d-1} represents the outward unit vector. By introducing a novel unified surface energy matrix G k ( n ) \boldsymbol {G}_k(\boldsymbol {n}) depending on γ ( n ) \gamma (\boldsymbol {n}) , the Cahn-Hoffman ξ \boldsymbol {\xi } -vector and a stabilizing function k ( n ) : S d − 1 → R k(\boldsymbol {n}):\ \mathbb {S}^{d-1}\to {\mathbb R} , we obtain a unified and conservative variational formulation for the anisotropic surface diffusion via different surface differential operators, including the surface gradient operator, the surface divergence operator and the surface Laplace-Beltrami operator. A SP-PFEM discretization is presented for the variational problem. In order to establish the unconditional energy stability of the proposed SP-PFEM under a very mild condition on γ ( n ) \gamma (\boldsymbol {n}) , we propose a new framework via local energy estimate for proving energy stability/structure-preserving properties of the parametric finite element method for the anisotropic surface diffusion. This framework sheds light on how to prove unconditional energy stability of other numerical methods for geometric partial differential equations. Extensive numerical results are reported to demonstrate the efficiency and accuracy as well as structure-preserving properties of the proposed SP-PFEM for the anisotropic surface diffusion with arbitrary anisotropic surface energy density γ ( n ) \gamma (\boldsymbol {n}) arising from different applications.

Oxy-difluoroallylation of Ynamides by Nickel-Catalyzed Tandem Alkoxylation/Claisen Rearrangement.

A nickel-catalyzed tandem alkoxylation/claisen rearrangement strategy for the oxy-difluoroallylation of ynamides has been developed. In this reaction, 3,3-difluoroallyl alcohol was used as a fluorine-containing building block to construct the C-CF2 bond for the first time. This approach is recognized for its robust tolerance of functional groups, impressive yields, and excellent atomic efficiency, all achieved under mild reaction conditions. A series of β,β-difluoromethyleneamide derivatives were efficiently obtained through simple operations, and their practicality was confirmed through gram-scale synthesis and product derivatization.

Regioselective Markovnikov hydrothiolation of 1-aryl-1,3-butadienes with dithiocarbamic acid to allyl dithiocarbamates.

A metal, ligand and solvent-free three component reaction of 1-aryl-1,3-butadienes, CS2 and amine has been developed. In this process, readily available CS2 and secondary amines were used for C-N and C-S bonds giving allyl dithiocarbamates with notable Markovnikov selectivity, mild reaction conditions, simple operation and compatibility with various functional groups (37 examples). This is first case of dithiocarbamic acid addition to an unsymmetrical 1,3-diene system.

Synergistic effect of Hypoxic Conditioning and Cell-Tethering Colloidal Gels enhanced Productivity of MSC Paracrine Factors and Accelerated Vessel Regeneration.

Microporous hydrogels have been widely used for delivering therapeutic cells. However, several critical issues, such as the lack of control over the harsh environment they are subjected to under pathological conditions and rapid egression of cells from the hydrogels, have produced limited therapeutic outcomes. To address these critical challenges, cell-tethering and hypoxic conditioning colloidal hydrogels containing mesenchymal stem cells (MSCs) are introduced to increase the productivity of paracrine factors locally and in a long-term manner. Cell-tethering colloidal hydrogels that are composed of tyramine-conjugated gelatin prevent cells from egressing through on-cell oxidative phenolic crosslinks while providing mechanical stimulation and interconnected microporous networks to allow for host-implant interactions. Oxygenating microparticlesencapsulated in tyramine-conjugated colloidal microgels continuously generated oxygen for 2 weeks with rapid diffusion, resulting in maintaining a mild hypoxic condition while MSCs consumed oxygen under severe hypoxia. Synergistically, local retention of MSCs within the mild hypoxic-conditioned and mechanically robust colloidal hydrogels significantly increased the secretion of various angiogenic cytokines and chemokines. The oxygenating colloidal hydrogels induced anti-inflammatory responses, reduced cellular apoptosis, and promoted numerous large blood vessels in vivo. Finally, mice injected with the MSC-tethered oxygenating colloidal hydrogels significantly improved blood flow restoration and muscle regeneration in a hindlimb ischemia (HLI) model.

NaOH-Assisted Multicomponent Reaction and Polymerizations of Elemental Sulfur, Diisocyanides, and Diols to Access Functional Poly(O-thiocarbamate)s.

Sulfur-containing polymers with unique structures and fascinating properties have attracted much attention recently, the efficient and economic synthetic approaches for various sulfur-containing polymers have rapidly developed. Herein, the multicomponent reaction of elemental sulfur, isocyanide, and alcohol was designed at mild condition with the assistance of NaOH, and the corresponding NaOH-assisted multicomponent polymerization of elemental sulfur, diisocyanides, and diols were developed at room temperature or 40 oC in air, to produce poly(O-thiocarbamate)s with well-defined structures, high molecular weights (Mws up to 32 500 g/mol) and high yields (up to 99%). The facilely available monomers, mild condition, and high efficiency of this MCP enabled scale-up synthesis of poly(O-thiocarbamate)s, and 7.34 g polymer was obtained in 98% yield. These functional poly(O-thiocarbamate)s could enrich Au3+ from aqueous solution with high enrichment capacity (983 mg·Au3+/g) and high efficiency (>99.99%) in 1 min, demonstrating superior gold enrichment performance and their potential industrial and economic values.

Insight into C4 Selectivity in the Light‐Driven C−H Fluoroalkylation of Pyridines and Quinolines

AbstractGiven the prevalence of pyridine motifs in FDA‐approved drugs, selective fluoroalkylation of pyridines and quinolines is essential for preparing diverse bioisosteres. However, challenges are often faced with conventional Minisci reactions in achieving precise regioselectivity owing to competing reaction sites of pyridine and the limited availability of fluoroalkyl radical sources. Herein, we present a light‐driven, C4‐selective fluoroalkylation of azines utilizing N‐aminopyridinium salts and readily available sulfinates. Our approach employs electron donor‐acceptor complexes, achieving highly C4‐selective fluoroalkylation under mild conditions without an external photocatalyst. This practical method not only enables the installation of CF2H groups but also allows for the incorporation of CF2‐alkyl groups with diverse functional entities, surpassing the limitations of previous methods. The versatility of the radical pathway is further demonstrated through straightforward three‐component reactions involving alkenes and [1.1.1]propellane. Detailed experimental and computational studies have elucidated the origins of regioselectivity, providing profound insights into the mechanistic aspects.

Convenient partial reduction of CO2 to a useful C1 building block: efficient access to 13C‐labelled N‐heterocyclic carbenes

The selective, transition metal‐free hydrosilylation of CO2 to CH2(OSiEt3)2 has been achieved under mild conditions and in high isolated yields (up to 90%) using Et3SiH and the simple, easily prepared borohydride catalyst Li+[HB(C6F5)3]−. The resulting CO2‐derived bis(silyl)acetal product – whose mechanism of formation has been interrogated through detailed computational and experimental studies – can be rapidly valorized through the facile synthesis of N‐heterocyclic carbenes, via their corresponding imidazolium salts. By using relatively inexpensive, isotopically enriched 13CO2 this protocol can be exploited to prepare NHC isotopologues that are selectively 13C labelled at the key, ligating C2 position. This provides an electronically responsive 13C NMR spectroscopic handle with dramatically enhanced sensitivity which can directly benefit reactivity studies in both organo‐ and organometallic catalysis, where NHC use is ubiquitous.

EnantioselectiveSynthesis ofspiro[indoline-3,4- pyrrolo [3,4-b]pyridines] via Organocatalysed Three-Component Cascade Reaction.

Asymmetric synthesis of spiro[indoline-3,4-pyrrolo [3,4-b]pyridines] derivatives was first developed through organocatalytic cascade Knoevenagel/Michael/cyclization reaction using a quinidine -derived squaramide. Under the optimized conditions, the three-component reaction of isatins, cyanoacetates, and 3-aminomaleimides yield the desired heterocycle-fused spirooxindoles in good yields (78-91%) with 53-99% enantiomer excess (ee). Notably, this reaction enabled a broad substrate scope under mild conditions, and provided a convenient method for enantioselective construction of diverse spirooxindoles combined with dihydropyridine and maleimide skeleton, which brought great potential to build new bioactive chemical entities.

An Effective Strategy to Boost Formic Acid Dehydrogenation over Pd/AC-NH2 Catalyst through Pd Size Control.

Formic acid (FA, HCOOH) is regarded as one of the most promising carriers for hydrogen storage. However, the catalyst design for FA dehydrogenation into H2 with high efficiency is not clear. Here, we elucidate the rationale of size effect over the most commonly used Pd-based catalyst through supporting different Pd species, including single atoms, nanoclusters, and nanoparticles, on amine-functionalized active carbon (Pd/AC-NH2). The activity test presents that Pd/AC-NH2 with Pd nanoclusters exhibits the best turnover frequency (TOF) value of 40856 h-1 for 1 M FA at 328 K and even 1504 h-1 for neat FA at 308 K, which is comparable to the homogeneous catalysts and has been the first heterogeneous catalyst used in neat FA dehydrogenation under mild conditions. The comprehensive characterizations reveal that the size of Pd species affects the ratios of Pd0/Pd2+ and hydrogen spillover effect, which is crucial for the C-H cleavage and H2 desorption. Besides, the influences of amine groups on catalytic performance were further examined. This work provided an ingenious guideline to design efficient and practical catalysts for hydrogen storage under ambient conditions.

Nickel/Photoredox-Catalyzed Asymmetric Three-Component Cross-Coupling To Access Enantioenriched 1,1-Diaryl(heteroaryl)alkanes.

An enantioselective 1,2-dicarbofunctionalization of vinyl (hetero)arenes with alkyl bromides and aryl bromides through nickel/photoredox catalysis is described. This three-component enantioselective domino alkyl arylation of vinyl (hetero)arenes could generate a diverse array of enantioenriched 1,1-diaryl(heteroaryl)alkanes with good to excellent yields (up to 88%) and high enantioselectivities (up to 99% ee). This transformation could proceed well under mild conditions with excellent chemo- and regioselectivity due to the avoidance of the use of air- and moisture-sensitive organometallic reagents and stoichiometric metal reductants. Mechanistic studies suggested that the alkyl radical is generated via NiI species or photocatalyst.

Visible-Light-Triggered Radical-Addition/Ring-Opening Cascade Reactions of 2H-Indazoles to Access ortho-Alkoxycarbonylated Azobenzenes.

A series of asymmetric azobenzenes have been synthesized by radical-addition/ring-opening cascade reactions from 2H-indazole in the presence of PIFA and alcohols under blue light irradiation and nitrogen protection. Furthermore, a wide range of functional groups were tolerated and the corresponding products were obtained in 30% to 95% isolated yields. The protocol is characterized by its visible-light initiation, avoidance of metals and photocatalysts, mild reaction conditions, and may find potential use in materials science and medicinal chemistry.

Synthesis of N2-Substituted 1,2,3-Triazoles.

We present a novel synthetic approach for the synthesis of the 1,2,3-triazole core, with a particular focus on the direct and regioselective synthesis of the synthetically more challenging triazoles having additional substituents at the N2 nitrogen atom. Through treatment of readily accessible geminal diazides with organic hydrazines under mild thermolysis conditions, a broad spectrum of N2-alkyl- and N2-aryl-1,2,3-triazoles are easily generated. For example, geminal diazides derived from ketoesters, ketoamides, and ketones were converted under the reaction conditions. The product structures were confirmed via NMR as well as single-crystal structure analysis.

Transition-Metal-Free Late-Stage Decarboxylative gem-Difluoroallylation of Primary Alkyl Acids.

A transition-metal-free late-stage decarboxylative gem-difluoroallylation of carboxylic acids with α-trifluoromethyl alkenes has been described by the use of organo-photoredox catalysis. Both primary alkyl and heteroaryl acids were readily incorporated. This approach merits feedstock materials, mild reaction conditions, and wide functionality tolerance. The synthetic utility of this approach has been highlighted by the late-stage functionalization of a variety of acid-containing natural products and drug molecules.

Visible-Light Photoredox-Catalyzed Direct Decarboxylative Functionalization of α-Keto Acids.

A novel and environmentally friendly photocatalytic strategy is presented for generating acyl radicals from benzoylformic acids, which are subsequently trapped by various sulfone-based SOMOphiles. This strategy provides a robust toolkit to access a variety of synthetically important functionalized aryl-ketone derivatives, which efficiently and directly construct acyl-S, acyl-Se, acyl-C, and acyl-N bonds. The broad substrate scope, excellent functional group compatibility, and mild reaction conditions make this protocol practical and attractive.

Conversion of Cellobiose to Formic Acid as a Biomass-Derived Renewable Hydrogen Source Using Solid Base Catalysts.

Formic acid is considered a promising hydrogen carrier. Biomass-derived formic acid can be obtained by oxidative decomposition of sugars. This study explored the production of formic acid from cellobiose, a disaccharide consisting of d-glucose linked by β-glycosidic bonds using heterogeneous catalysts under mild reaction conditions. The use of alkaline earth metal oxide solid base catalysts like CaO and MgO in the presence of hydrogen peroxide could afford formic acid from cellobiose at 343 K. While CaO gave 14 % yield of formic acid, the oxide itself was converted to a harmful metal peroxide, CaO2 after the reaction. In contrast, MgO could produce formic acid without the formation of the metal peroxide. The difficulty in selectively synthesizing formic acid from cellobiose using these solid base catalysts was due to the poor conversion of cellobiose to glucose. Using a combination of solid acid and base catalysts, a high formic acid yield of 33 % was obtained under mild reaction conditions due to the quantitative hydrolysis of cellobiose to glucose by a solid acid followed by the selective decomposition of glucose to formic acid by a solid base.