Acid-catalyzed Research Articles

Catalytic Fatty Acid Methyl Esters (FAMEs) Synthesis Using Lepidium aucheri Seed Oil and Its Antibacterial Potential

Catalytic Fatty Acid Methyl Esters (FAMEs) Synthesis Using Lepidium aucheri Seed Oil and Its Antibacterial Potential

Regio- and Stereoselective Construction of 1,3,5-Triaroylcyclohexanes via KOtBu-Mediated Cyclotrimerization of Aryl Vinyl Ketones.

Herein, we disclose a simple one-pot method for an efficient regio- and stereoselective synthesis of 1,3,5-triaroylcyclohexanes from aryl vinyl ketones using potassium tert-butoxide. The developed protocol allows the construction of various symmetrically substituted cyclohexanes in good to excellent yields. The major product 2 also can be converted to the product 3 (all equatorial) conveniently by acid catalysis. This protocol features a good substrate scope and functional group compatibility.

Effect of a Thermomechanical Pretreatment Coupled to Sulfuric Acid or Sodium Hydroxide Catalysis on Physicochemical Properties and Enzymatic Hydrolysis of Alfa Fibers (Stipa tenacissima L.)

Effect of a Thermomechanical Pretreatment Coupled to Sulfuric Acid or Sodium Hydroxide Catalysis on Physicochemical Properties and Enzymatic Hydrolysis of Alfa Fibers (Stipa tenacissima L.)

Promoting Cl2O Generation from the HOCl + HOCl Reaction on Aqueous/Frozen Air-Water Interfaces.

Hypochlorous acid (HOCl) is considered a temporary reservoir of dichlorine monoxide (Cl2O). Previous studies have suggested that Cl2O is difficult to generate from the reaction of HOCl + HOCl in the gas phase. Here, we demonstrate that Cl2O can be generated from the HOCl + HOCl reaction at aqueous/frozen air-water interfaces, which is confirmed by ab initio molecular dynamic calculations. Distinct from the one-step reaction in the gas phase, our results show that Cl2O generation from HOCl + HOCl on aqueous/frozen interfaces involves two elementary steps, namely, one HOCl deprotonation and one Cl-abstraction from the other HOCl. Specifically, the mechanisms of neutral/acidic catalysis from interfacial water/nitric acid and base catalysis from ammonia, methylamine and dimethylamine have been examined. For the former, HOCl deprotonation is the rate-limiting step, and the total k of Cl2O generation increases to 9.23 × 10-9-9.10 × 10-1 M-1 s-1 at the aqueous interface and 3.20 × 10-7-4.10 × 10-3 M-1 s-1 at the frozen interface, which is at least 23 and 25 orders of magnitude greater than that of gaseous k (3.31 × 10-32 M-1 s-1). For the latter, the rate-limiting step is changed to Cl-abstraction, whose total k dramatically increases to 1.40-8.97 × 107 M-1 s-1 at the aqueous interface and 7.12-9.99 × 106 M-1 s-1 at the frozen interface. Interestingly, the Cl2O production rates ranked in the order of dimethylamine < methylamine < ammonia and decreased with increasing catalytic alkalinity. These findings provide new insights for understanding other Cl2O sources beyond the ClONO2 + HOCl reaction.

The role of ACSL4 in stroke: mechanisms and potential therapeutic target.

Stroke, as a neurological disorder with a poor overall prognosis, has long plagued the patients. Current stroke therapy lacks effective treatments. Ferroptosis has emerged as a prominent subject of discourse across various maladies in recent years. As an emerging therapeutic target, notwithstanding its initial identification in tumor cells associated with brain diseases, it has lately been recognized as a pivotal factor in the pathological progression of stroke. Acyl-CoA synthetase long-chain family member 4 (ACSL4) is a potential target and biomarker of catalytic unsaturated fatty acids mediating ferroptosis in stroke. Specifically, the upregulation of ACSL4 leads to heightened accumulation of lipid peroxidation products and reactive oxygen species (ROS), thereby exacerbating the progression of ferroptosis in neuronal cells. ACSL4 is present in various tissues and involved in multiple pathways of ferroptosis. At present, the pharmacological mechanisms of targeting ACSL4 to inhibit ferroptosis have been found in many drugs, but the molecular mechanisms of targeting ACSL4 are still in the exploratory stage. This paper introduces the physiopathological mechanism of ACSL4 and the current status of the research involved in ferroptosis crosstalk and epigenetics, and summarizes the application status of ACSL4 in modern pharmacology research, and discusses the potential application value of ACSL4 in the field of stroke.

Improved Hydrothermal Conversion of Pea Pod Biomass for Production of Platform Chemicals with Organic Acid Catalysts

Agro-industries produce over 2 billion tons of agricultural waste annually, including by-products like bagasse, molasses, seeds, stems, leaves, straw, and shells. The use of agro-industrial waste is a way to reduce the impact of industrial processes on the environment. The pea pod is a biomass with a high concentration of cellulose, hemicellulose and some lignin; therefore, it can be used to produce platform chemicals by means of a hydrothermal process. There is limited research on the hydrolysis of pea biomass, but it has been shown to obtain high yields. This study analyzed the effectiveness and selectivity of the hydrothermal process using pea pod biomass with a particle size of 0.5 mm at 180 °C for one hour. A 500 mL reactor was used, with a biomass-to-acid solution ratio of 1:20. The concentration of the acid solution was 0.02 M. The concentrations of sugar, formic acid, levulinic acid, HMF, and furfural produced were measured. Among the catalysts studied, adipic acid catalysis showed the highest yield of 65.16%, with 37.09% of sugar, 16.37% of formic acid, and 11.71% of levulinic acid. On the other hand, the catalysts with chloroacetic acid, butyric acid, anthranilic acid, and phthalic acid were less effective but demonstrated selectivity for sugar production, proving that the liquid phase obtained using the catalyst with those acids can be used as carbon sources for a fermentation process. In general, when comparing the process with or without the use of a catalyst, it is observed that with a catalyst in the reaction, the amount of HMF and furfural produced is reduced and the selectivity with respect to sugar production is increased.

Organocatalytic Asymmetric Cascade Bicyclization of 2‐Indolylmethanols with α‐(2‐Indolyl) Propargylic Alcohols to Access Chiral Fluorescent Hexacyclic Bisindoles

AbstractA cascade regioselective 1,8‐addition/biscyclization of 2‐indolylmethanols with α‐(2‐indolyl) propargylic alcohols has been developed via chiral phosphoric acid (CPA) catalysis. A series of chiral cyclopenta[4,5]pyrrolo biindoles bearing a quaternary stereogenic center were obtained in modest to good yields (72–95%) with high enantioselectivities (82–94%). Additionally, the photophysical properties of these hexacyclic bisindoles are examined, revealing bright fluorescence with high quantum yields.

Loading Lewis Acid/Base Pair on Metal Nanocluster for Catalytic Ugi Reaction

AbstractConstructing structurally robust and catalytically active metal nanoclusters for catalyzing multi‐component reactions is an interesting while challenging task. Inspired by Lewis acid and Lewis base catalysis, we realized the combination of both Lewis acid and Lewis base sites on the surface of a stable gold nanocluster Au35Cd2. The catalytic potential of Au35Cd2 in four‐component Ugi reaction was explored, demonstrating high activity and exceptional recyclability. In‐depth mechanism studies indicate that the catalytic synergy of the Lewis acid/base pair is crucial for the high efficiency of Au35Cd2‐catalyzed Ugi reaction. Bearing the stable structure, multiple activation sites and hierarchical chirality, Au35Cd2 is expected to display further interesting catalytic performance such as asymmetric catalysis.

Recognition of a salivary effector by the TNL protein RCSP promotes effector-triggered immunity and systemic resistance in Nicotiana benthamiana.

Insects secret chemosensory proteins (CSPs) into plant cells as potential effector proteins during feeding. The molecular mechanisms underlying how CSPs activate plant immunity remain largely unknown. We show that CSPs from six distinct insect orders induce dwarfism when overexpressed in Nicotiana benthamiana. Agrobacterium-mediated transient expression of Nilaparvata lugens CSP11 (NlCSP11) triggered cell death and plant dwarfism, both of which were dependent on ENHANCED DISEASE SUSCEPTIBILITY 1 (EDS1), neuregulin 1 (NRG1) and SENESCENCE-ASSOCIATED GENE 101 (SAG101), indicating the activation of effector-triggered immunity (ETI) in N. benthamiana. Overexpression of NlCSP11 led to stronger systemic resistance against Pseudomonas syringae DC3000 lacking effector HopQ1-1 and tobacco mosaic virus, and induced higher accumulation of salicylic acid (SA) in uninfiltrated leaves compared to another effector XopQ that is recognized by a Toll-interleukin-1 receptor (TIR) domain nucleotide-binding leucine-rich repeat receptor (TNL) called ROQ1 in N. benthamiana. Consistently, NlCSP11-induced dwarfism and systemic resistance, but not cell death, were abolished in N. benthamiana transgenic line expressing the SA-degrading enzyme NahG. Through large-scale virus-induced gene silencing screening, we identified a TNL protein that mediates the recognition of CSPs (RCSP), including aphid effector MP10 that triggers resistance against aphids in N. benthamiana. Co-immunoprecipitation, bimolecular fluorescence complementation and AlphaFold2 prediction unveiled an interaction between NlCSP11 and RCSP. Interestingly, RCSP does not contain the conserved catalytic glutamic acid in the TIR domain, which is required for TNL function. Our findings point to enhanced ETI and systemic resistance by a TNL protein via hyperactivation of the SA pathway. Moreover, RCSP is the first TNL identified to recognize an insect effector.

Post-functionalized cellulose/metal-organic framework composite with sulfonic acid: An efficient, rapid and recyclable bio-based solid acid catalyst for the synthesis of 5-hydroxymethylfurfural

A new acid catalyst derived from renewable sources was developed using an ultrasound-assisted approach. This involved the formation of a metal-organic framework called MIL-88(Fe) in the presence of carboxymethylated-cellulose (CMC). Subsequently, the catalyst underwent a post-synthetic modification to introduce further acidic –SO3H groups into the structure of the CMC/MIL-88(Fe) composite. Various examinations were carried out that validated the successful creation of the CMC/MIL-88(Fe)-SO3H catalyst. The effectiveness of the catalyst was assessed in the process of solid acid catalysis, specifically in the dehydration of fructose to produce 5-hydroxymethylfurfural (HMF). Through the employment of Response Surface Method (RSM) optimization, it was determined that utilizing 34 wt% of the catalyst at a temperature of 90 °C for 30 min resulted in a remarkable 98 % HMF yield. The catalyst exhibited good reusability, as it retained its catalytic effectiveness throughout four consecutive cycles. Comparative catalytic investigations involving CMC and CMC/MIL-88(Fe) composite without sulfonation revealed the superior activity of CMC/MIL-88(Fe)-SO3H catalyst, emphasizing the collaborative effect of CMC, MIL-88(Fe), and the impact of post-functionalization with -SO3H on the performance of the catalyst.

A Sustainable and Green Approach to the Preparation of Hantzsch-1,4-Dihydropyridines Using Phytic Acid Catalysis

A Sustainable and Green Approach to the Preparation of Hantzsch-1,4-Dihydropyridines Using Phytic Acid Catalysis

Diastereoselective Intramolecular Spirocyclization via C(sp3)‐H Bond Functionalization Towards the Synthesis of 2,7‐Diazaspiro[4.5]decane‐1,3‐diones

The C(sp3)‐H functionalization via intramolecular hydride transfer initiated cascade annulation for the synthesis of spiro‐fused succinimide‐containing tetrahydroquinolines induced by iminium intermediates is described. A series of diastereoselective 2,7‐diazaspiro[4.5]decanes‐1,3‐diones were achieved using ortho‐amino‐benzylidene‐succinimide using Lewis acid catalysis. This scandium triflate Sc(OTf)3 catalysed, oxidant‐free protocol leads to the diastereoselective synthesis of a class of 2,7‐diazaspiro[4.5]decanes‐1,3‐diones derivatives with 48‐98% yield in a single step.

Organocatalytic Asymmetric [3 + 2] Cyclization: Enantioselective Synthesis of α-Indolyl Pyrrolo[1,2-a]indole Scaffolds.

A novel asymmetric [3 + 2] cyclization of α-indolyl propargylic alcohols with 3-alkyl-1H-indoles via chiral phosphoric acid catalysis has been established. This strategy allowed the synthesis of chiral α-indolyl pyrrolo[1,2-a]indole derivatives with high yields (up to 91%) and excellent enantioselectivities (up to 99% ee), facilitating both the reaction activity and enantioselectivity by using the solvent of CH3CFCl2. Significantly, this protocol will provide an effective synthetic approach for constructing enantioenriched α-indolyl pyrrolo[1,2-a]indole cores of antimalarial natural product isoborreverine analogues.

Selective C-N Bond Cleavage in Unstrained Pyrrolidines Enabled by Lewis Acid and Photoredox Catalysis.

Cleavage of inert C-N bonds in unstrained azacycles such as pyrrolidine remains a formidable challenge in synthetic chemistry. To address this, we introduce an effective strategy for the reductive cleavage of the C-N bond in N-benzoyl pyrrolidine, leveraging a combination of Lewis acid and photoredox catalysis. This method involves single-electron transfer to the amide, followed by site-selective cleavage at the C2-N bond. Cyclic voltammetry and NMR studies demonstrated that the Lewis acid is crucial for promoting the single-electron transfer from the photoredox catalyst to the amide carbonyl group. This protocol is widely applicable to various pyrrolidine-containing molecules and enables inert C-N bond cleavage including C-C bond formation via intermolecular radical addition. Furthermore, the current protocol successfully converts pyrrolidines to aziridines, γ-lactones, and tetrahydrofurans, showcasing its potential of the inert C-N bond cleavage for expanding synthetic strategies.

Unified Enantioselective Allylations and Vinylogous Reactions Enabled by Visible Light-Driven Chiral Lewis Acid Catalysis

Unified Enantioselective Allylations and Vinylogous Reactions Enabled by Visible Light-Driven Chiral Lewis Acid Catalysis

Stereocontrolled Synthesis of 1,4-Dicarbonyls via [3,3]-Sulfonium Rearrangement and Application to the Synthesis of Heterocycles

Due to an inherent polarity mismatch of the corresponding retrosynthetic synthons, 1,4-dicarbonyl synthesis through polar pathways requires a retrosynthetic rethink. While Umpolung-based approaches exist, efficient control of both the absolute and relative configuration of newly formed stereogenic centres within this motif has long proven particularly challenging. In this Synpacts, we highlight our work on the stereodivergent synthesis of 1,4-dicarbonyl compounds through an unusual transformation that relies on vinyl sulfoxides and ynamides as reactants. This method allows stereoselective access to each and every one out of the four possible stereoisomers of a generic 1,4-dicarbonyl target in a process where enantio- and diastereoselectivity are “dialled into” the vinyl sulfoxide partner. Recent studies show that the thus formed 1,4-dicarbonyls serve as excellent linchpins for structural diversification into highly substituted heterocycles, including those found in natural products. 1. Introduction 2. Synthesis of 1,4-dicarbonyl compounds under acid catalysis 3. Cyclisation towards γ-lactones and γ-lactams 4. Application in total synthesis 5. Conclusion

Modular Synthesis of Azidobicyclo[2.1.1]hexanes via (3 + 2) Annulation of α-Substituted Vinyl Azides and Bicyclo[1.1.0]butanes.

Here, we present a mild and rapid method to access azidobicyclo[2.1.1]hexanes via formal (3 + 2) cycloaddition of α-substituted vinyl azides and bicyclo[1.1.0]butanes under Lewis acid catalysis. A wide range of α-substituted vinyl azides were tolerated under mild conditions. Notably, the resulting cycloadducts could be transformed into structurally attractive 3-azabicyclo[3.1.1]heptenes through microwave-promoted rearrangement. The utilities were highlighted by copper(I)-catalyzed Huisgen 1,3-dipolar cycloaddition of tertiary alkyl azide and further transformation of the azide and ketone groups.

Urea‐based construction of hydrogen bonding networks for poly(biphenyl alkylene)s anion exchange membrane for fuel cells

AbstractIn recent decades, the “trade‐off” problem of anion exchange membranes (AEMs) has been a concern. Herein, a series of urea‐based multication poly(biphenyl alkylene)s AEMs are prepared by obtaining an ether bond‐free backbone through ultra‐strong acid catalysis, grafting it with multication side chains, and then by accessing urea‐based groups in different ratios. By accessing the urea group, noncovalent bonds are used to link the molecules to act as cross‐links, giving them solubility that chemical cross‐links do not have. The PBTA‐DQA‐35U membrane possessed the highest ionic conductivity of 62.43 mS/cm. Compared with the PBTA‐DQA membrane (80°C, WU = 20.45%, SR = 17.67%), the PBTA‐DQA‐25U membrane showed an increase in water uptake but not much change in swelling (WU = 30.23%, SR = 19.36%), which was attributed to the fact that the hydrophilic urea groups provide cation transport sites while hydrogen bonding inhibits membrane swelling. The PBTA‐DQA‐35U ionic conductivity is retained above 75% after 960 h of alkali stability testing. The power density of the MEA device assembled using PBTA‐DQA‐35U membrane is 421.78 mW/cm2.

Enantioselective Synthesis of Axially Chiral Silacyclohexylidene Oxime Ethers by Chiral Phosphoric Acid Catalysis

The first asymmetric condensation of prochiral silacyclohexanones with hydroxylamines is developed by chiral phosphoric acid catalysis, which provided a facile and straightforward protocol for the enantioselective construction of valuable axially chiral silacyclohexylidene oxime ethers that are otherwise inaccessible. Notably, this constitutes a rare example for accessing silacycles featuring an axial chirality.

Preparation and Characterization of Glucose-Based Self-Blowing Non-Isocyanate Polyurethane (NIPU) Foams with Different Acid Catalysts.

The preparation and application of non-isocyanate polyurethane (NIPU) from biomass raw materials as a substitute for traditional polyurethane (PU) has recently become a research hot topic as it avoids the toxicity and moisture sensitivity of isocyanate-based PU. In the work presented here, self-blowing GNIPU non-isocyanate polyurethane (NIPU) rigid foams were prepared at room temperature, based on glucose, with acids as catalysts and glutaraldehyde as a cross-linker. The effects of different acids and glutaraldehyde addition on foam morphology and properties were investigated. The water absorption, compressive resistance, fire resistance, and limiting oxygen index (LOI) were tested to evaluate the relevant properties of the foams, and scanning electron microscopy (SEM) was used to observe the foams' cell structure. The results show that all these foams have a similar apparent density, while their 24 h water absorption is different. The foam prepared with phosphoric acid as a catalyst presented a better compressive strength compared to the other types prepared with different catalysts when above 65% compression. It also presents the best fire resistance with an LOI value of 24.3% (great than 22%), indicating that it possesses a good level of flame retardancy. Thermogravimetric analysis also showed that phosphoric acid catalysis slightly improved the GNIPU foams' thermal stability. This is mainly due to the flame-retardant effect of the phosphate ion. In addition, scanning electron microscopy (SEM) results showed that all the GNIPU foams exhibited similar open-cell morphologies with the cell pore sizes mainly distributed in the 200-250 μm range.