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We have developed a TfOH-catalyzed, highly efficient protocol for the synthesis of biologically active β-acylamino ketones from aldehyde, ketone, and nitrile by avoiding the use of acetyl chloride. The reaction proceeds through a sequential aldol reaction followed by a nucleophilic attack of nitrile and hydrolysis of nitrile in one pot. The attractive features of this tandem process are mild reaction conditions, high atom economy, broad substrate scope with 51–87% yield, gram-scale reaction, and ease of operation. [ABSTRACT FROM AUTHOR]

Herein, we report a metal-free, base-promoted route for the synthesis of hybrid molecular scaffolds in which various 1,3-diones and 1,2,4-triazoles are linked by a benzyl bridge. This three-component, one-pot reaction was accomplished by first treating 4-hydroxycoumarin, trans-β-nitrostyrene, and aldehyde hydrazone in the presence of sodium carbonate. Further, this protocol was successfully expanded to other 1,3-diones, such as dimedone and 4-hydroxy-2-quinolone. A broad substrate scope, mild reaction conditions, and the metal and ligand/additive-free approach are the prominent features of this strategy. [ABSTRACT FROM AUTHOR]

ABSTRACT Treatment of Ru3(CO)12 with salicylaldimine ligands [ArNCH(3‐tBuC6H3OH) [ArC6H5 (L1H); 4‐OMeC6H4 (L2H); 4‐MeC6H4 (L3H); 2,4,6‐Me3C6H2 (L4H); 4‐ClC6H4 (L5H); 4‐BrC6H4 (L6H)] in refluxing toluene afforded six bis‐ligand mononuclear ruthenium carbonyl complexes [ArNCH(3‐tBuC6H3O)]2Ru(CO)2 1a–1f in good yields. All of the Ru(II) complexes were characterized using IR, NMR, and elemental analysis. The molecular structures of complexes 1a, 1b, 1e, and 1f were further confirmed through X‐ray diffraction analysis. Additionally, the catalytic performance of these complexes was investigated in the oxidation of olefins to aldehydes, using TBHP as the oxidant in refluxing trichloromethane. With 1.0 mol% catalyst loading, these ruthenium complexes displayed high reactivity and good functional‐group compatibility, selectivity providing the corresponding oxidation product aldehydes in 73%–94% yields. [ABSTRACT FROM AUTHOR]

Schiff bases are a class of synthetic compounds that form when primary amines combine with aldehydes or ketones. These compounds are incredibly important across various fields, such as biology, catalysis, and optics, due to their diverse features. One notable aspect is their ability to form complexes with transition metals, which opens up a wide range of potential uses, particularly in human systems. In the human body, Schiff base metal complexes display a range of biological actions, including antibacterial, antifungal, anticancer, and antimalarial properties. The versatility of Schiff bases in reacting with different transition metals gives these complexes intriguing potential for addressing biological issues and treating diseases. This article explores various examples of Schiff bases, metal complexes, and their associated ligands, highlighting their usefulness in a variety of biological applications. The potential of Schiff base metal complexes as valuable agents in resolving medical difficulties and advancing biomedical research is emphasized. [ABSTRACT FROM AUTHOR]

The substituted tetrahydrofuran core is a structural motif in many biologically active and natural compounds. However, the scarcity of enantioselective methods developed towards its synthesis makes this field challenging and attractive to explore. Herein, the first Brønsted‐base catalyzed enantioselective (3+2) annulation of donor‐acceptor cyclopropanes with aldehydes and ketones affording enantioenriched 2,3,5‐substituted tetrahydrofurans is reported. The reaction concept is based on activation of racemic β‐cyclopropyl ketones by a chiral bifunctional Brønsted base which catalyzes the (3+2) annulation for a range of aldehydes and ketones. For aldehydes, the annulation furnished tetrahydrofurans in excellent yield, good diastereoselectivity and with excellent enantioselectivity up to >99 % ee. Surprisingly, aromatic aldehydes afforded the cis‐2,5‐substituted tetrahydrofurans as the major diastereoisomer, while for aliphatic aldehydes the trans‐cycloadduct was favored. The reaction also proceeds well for ketones affording spiro tetrahydrofurans in excellent yields and enantioselectivities (up to 99 % ee). Hammett studies have been conducted to elucidate the influence of the electronic nature of benzaldehydes on the stereoselectivity. Based on the diastereochemical outcome for the aldehydes, two reaction paths for aromatic and aliphatic aldehydes are proposed. Finally, two diastereoselective synthetic transformations have been conducted to demonstrate the synthetic potential of the obtained products. [ABSTRACT FROM AUTHOR]

An efficient and eco-friendly procedure was developed for the synthesis of N -aryl-2-((3-aryl-1,2,4-oxadiazol-5-yl)thio)acetamides from N -aryl-2-thiocyanatoacetamides and substituted N -hydroxybenzimidoyl chlorides that were prepared easily from the commercially available anilines and aryl aldehydes, respectively. The N -aryl-2-thiocyanatoacetamide acts as a dipolarophile while the nitrile oxide formed in situ from substituted N -hydroxybenzimidoyl chloride acts as the nucleophilic partner in a 1,3-dipolar cycloaddition reaction mediated by triethylamine base in ethanol medium. The procedure affords excellent yields of desired products containing electron-withdrawing and electron-donating groups on the aromatic rings, in short reaction time with ease of operation. The procedure for the synthesis of scaffolds that are potentially valuable for their biological properties also offers the possibility of scale-up to higher quantities. [ABSTRACT FROM AUTHOR]

Copyright of Shipin Kexue/ Food Science is the property of Food Science Editorial Department and its content may not be copied or emailed to multiple sites or posted to a listserv without the copyright holder's express written permission. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)

Here we report a transition metal– and oxidant–free annulation cascade method for the synthesis of chromeno–isoxazoles. The annulation reaction involves easily accessible starting materials, 3‐nitro‐2H‐chromene and α‐chloro aldehyde, yielding the structurally intriguing framework, chromeno[3,4‐c]isoxazoles employed by tripotassium phosphate as a base. The isoxazole ring construction over the 2H–chromene unit is believed to occur via a series of multiple reaction sequences. Here, the enolate generation/Michael addition/C−Cl bond cleavage/oxy–anionic addition to reactive tethered‐aldehyde/deformylation via retro–C−C and N−O bond cleavages are the most possible sequences which furnish the desired end–product in good chemical yields. The multiple reaction sequences occur in one‐pot at mild conditions, supported by experimental results and a few control experiments including DFT studies. This process exhibits a broad substrates scope illustrating good functional group compatibility towards both the nitrochromenes and aldehydes, and thus prove to be a general and efficient protocol for the synthesis of chromeno[3,4–c]isoxazoles. Overall, the use of nitrochromene as the limiting reagent, noteworthy functional group tolerance, scalability including great applications like chiral pool strategy towards the synthesis of enantioenriched chromeno‐isoxazole are the additional features. [ABSTRACT FROM AUTHOR]

The selective and controllable functionalization of unreactive C(sp3)–H bonds under mild conditions is a highly desirable yet challenging goal in both organic synthesis and pharmaceutical industry. Herein, we report an unprecedented visible-light mediated metal- and oxidant-free carbonylation of both benzylic and allylic C–H bonds with H2O. The synergistic combination of an organophotocatalyst 4CzIPN and a thiol enables the transformation of diverse arrays of benzylic and allylic C–H bonds into carbonyls in moderate to excellent yields with good functional group compatibility. Moreover, the oxidation of amines to aldehydes has also been realized by this protocol. Mechanistically, an oxidative radical-polar crossover (ORPC) process affords an alcohol intermediate, which then undergoes another ORPC process to furnish the carbonyl product. [ABSTRACT FROM AUTHOR]

A photocatalytic trifluoromethylation/cyclization reaction of N-allyl and N-homoallyl aldehyde hydrazones with trifluoromethyl thianthrenium triflate was developed for the synthesis of trifluoromethylated dihydropyrazoles and tetrahydropyridazines. Besides, PhI(O2CCHF2)2 was employed to realize the construction of difluoromethylated dihydropyrazoles and tetrahydropyridazines. These protocols exhibit a broad substrate scope and good functional group tolerance. [ABSTRACT FROM AUTHOR]

Poria cocos (Schw.) wolf (P. cocos) is an important medicinal material with both therapeutic and edible properties. This study investigated volatile constituents, amino acids, proteins, polysaccharides, triterpenoid ingredients, and alcohol-soluble extracts on P. cocos during eight drying processes. A total of 47 volatile components were found and identified; the main volatile components of shade drying (SD) and hot-air drying at 50 °C (HD50) were esters and alcohols, while for drying in hot air at 60 °C~100 °C (△ = 10 °C) and infrared drying (ID), the main compounds were aldehydes and hydrocarbons. The amino acids in P. cocos remained the same when dried with various methods. Compared with SD samples, with the temperature increase, the content of amino acids showed a trend of first decreasing and then increasing, while the content trend of proteins was the opposite. The HD70 samples had the highest content of polysaccharide, triterpenoid ingredients, alcohol-soluble extracts, and antioxidant activity. Furthermore, volatile compounds showed a correlation between non-volatile constituents. This research provides evidence that the aroma, active components, and activity of P. cocos were affected by the drying method. [ABSTRACT FROM AUTHOR]

Electronic nicotine delivery systems (ENDS) aerosol exposures can induce endothelial dysfunction (ED) in healthy young humans and animals. Thermal degradation of ENDS solvents, propylene glycol, and vegetable glycerin (PG: VG), generates abundant formaldehyde (FA) and other carbonyls. Because FA can activate the transient receptor potential ankyrin-1 (TRPA1) sensor, we hypothesized that FA in ENDS aerosols provokes TRPA1-mediated changes that include ED and "respiratory braking"—biomarkers of harm. To test this, wild-type (WT) and TRPA1-null mice were exposed by inhalation to either filtered air, PG: VG-derived aerosol, or FA (5 ppm). Short-term exposures to PG: VG and FA-induced ED in female WT but not in female TRPA1-null mice. Moreover, acute exposures to PG: VG and FA stimulated respiratory braking in WT but not in TRPA1-null female mice. Urinary metabolites of FA (ie, N - 1,3-thiazolidine-4-carboxylic acid, TCA; N - 1,3-thiazolidine-4-carbonyl glycine, TCG) and monoamines were measured by LC-MS/MS. PG: VG and FA exposures significantly increased urinary excretion of both TCA and TCG in both WT and TRPA1-null mice. To confirm that inhaled FA directly contributed to urinary TCA, mice were exposed to isotopic 13C-FA gas (1 ppm, 6 h). 13C-FA exposure significantly increased the urine level of 13C-TCA in the early collection (0 to 3 h) supporting a direct relationship between inhaled FA and TCA. Collectively, these data suggest that ENDS use may increase CVD risk dependent on FA, TRPA1, and catecholamines, yet independently of either nicotine or flavorants. This study supports that levels of FA in ENDS-derived aerosols should be lowered to mitigate CVD risk in people who use ENDS. [ABSTRACT FROM AUTHOR]

SUMMARY: Among the three active aldehyde oxidases in Arabidopsis thaliana leaves (AAO1‐3), AAO3, which catalyzes the oxidation of abscisic‐aldehyde to abscisic‐acid, was shown recently to function as a reactive aldehyde detoxifier. Notably, aao2KO mutants exhibited less senescence symptoms and lower aldehyde accumulation, such as acrolein, benzaldehyde, and 4‐hydroxyl‐2‐nonenal (HNE) than in wild‐type leaves exposed to UV‐C or Rose‐Bengal. The effect of AAO2 expression absence on aldehyde detoxification by AAO3 and/or AAO1 was studied by comparing the response of wild‐type plants to the response of single‐functioning aao1 mutant (aao1S), aao2KO mutants, and single‐functioning aao3 mutants (aao3Ss). Notably, aao3Ss exhibited similar aldehyde accumulation and chlorophyll content to aao2KO treated with UV‐C or Rose‐Bengal. In contrast, wild‐type and aao1S exhibited higher aldehyde accumulation that resulted in lower remaining chlorophyll than in aao2KO leaves, indicating that the absence of active AAO2 enhanced AAO3 detoxification activity in aao2KO mutants. In support of this notion, employing abscisic‐aldehyde as a specific substrate marker for AAO3 activity revealed enhanced AAO3 activity in aao2KO and aao3Ss leaves compared to wild‐type treated with UV‐C or Rose‐Bengal. The similar abscisic‐acid level accumulated in leaves of unstressed or stressed genotypes indicates that aldehyde detoxification by AAO3 is the cause for better stress resistance in aao2KO mutants. Employing the sulfuration process (known to activate aldehyde oxidases) in wild‐type, aao2KO, and molybdenum‐cofactor sulfurase (aba3‐1) mutant plants revealed that the active AAO2 in WT employs sulfuration processes essential for AAO3 activity level, resulting in the lower AAO3 activity in WT than AAO3 activity in aao2KO. Significance Statement: The current study demonstrates that impairment of AAO2 causes enhancement of AAO3 activity and carbonyl aldehyde detoxification increase in Arabidopsis. [ABSTRACT FROM AUTHOR]

Aldehyde decarbonylation is a vital chemical transformation in the synthesis of natural products. Nature accomplishes this process through a family of decarbonylase enzymes, while in the laboratory, harsh transition metals and elevated temperatures are required. Herein, we report a mild aldehyde decarbonylation reaction that exhibits exclusive selectivity for ortho -aldehydes during a tandem nitrile boronic acid cross-coupling reaction. A wide substrate scope is displayed that includes regioselective removal of the ortho -aldehyde from phenyl boronic acids in the presence of meta - or para -aldehydes. A mechanistic investigation of the observed regioselectivity for ortho -aldehydes by density functional theory (DFT) calculations shows that the CO ligand extrusion is energetically more favorable for the ortho position as compared to the para position. [ABSTRACT FROM AUTHOR]

Two novel synthetic routes to 4‐(N‐Boc‐N‐methylaminomethyl)benzaldehyde, an important pharmaceutical starting material, were developed using terephthaloyl chloride and terephthalaldehyde. In the first approach, terephthaloyl chloride was converted to an ester amide. The treatment of the ester amide with LiAlH4 followed by protection of the resulting amine with tert‐butoxycarbonyl anhydride yielded the corresponding benzyl alcohol. The benzyl alcohol was oxidized to the aldehyde completing the first‐generation synthesis. The second approach utilized a one‐step protocol mono‐selective reductive amination of terephthalaldehyde with N‐Boc‐methylamine using chlorodimethylsilane. Both methods were scalable to 50 mmol and provided the desired aldehyde in a synthetically useful yield, demonstrating their practicality. [ABSTRACT FROM AUTHOR]

Purple-fleshed sweetpotatoes (PFSPs) are rich in anthocyanins and are one of the health foods of interest. In this study, the effects of steaming on the anthocyanin, starch, soluble sugar, volatile organic compounds (VOCs) and pasting properties of nine PFSPs from China were investigated. The anthocyanin content of raw PFSP ranged from 9 to 185 mg/100 g. The total starch content decreased and soluble sugar content increased in all purple potatoes after steaming. Among the nine PFSPs varieties, Guangshu20 showed the greatest decrease in starch content (30.61%) and the greatest increase in soluble sugar content (31.12%). The pasting properties affected the taste of the PFSPs, with Shuangpihuang having the lowest peak viscosity (720.33 cP) and Guangzishu12 having the highest peak viscosity (2501.67 cP). Correlation studies showed that the anthocyanin content and pasting properties were negatively correlated with most of the sensory indicators, whereas the soluble sugar content of steamed PFSPs was significantly positively correlated with sweetness. A total of 54 VOCs were identified in this study, and aldehydes and terpenoids were the major VOCs in PFSPs. This study provides a theoretical basis for the processing of different PFSP varieties. [ABSTRACT FROM AUTHOR]

Aldehyde exposure has been shown to lead to the formation of DNA damage comprising of DNA-protein crosslinks (DPCs), base adducts and interstrand or intrastrand crosslinks. DPCs have recently drawn more attention because of recent advances in detection and quantification of these adducts. DPCs are highly deleterious to genome stability and have been shown to block replication forks, leading to wide-spread mutagenesis. Cellular mechanisms to prevent DPC-induced damage include excision repair pathways, homologous recombination, and specialized proteases involved in cleaving the covalently bound proteins from DNA. These pathways were first discovered in formaldehyde-treated cells, however, since then, various other aldehydes have been shown to induce formation of DPCs in cells. Defects in DPC repair or aldehyde clearance mechanisms lead to various diseases including Ruijs-Aalfs syndrome and AMeD syndrome in humans. Here, we discuss recent developments in understanding how aldehydes form DPCs, how they are repaired, and the consequences of defects in these repair pathways. [ABSTRACT FROM AUTHOR]

The catalytic direct hydroarylation of alkynamides is a highly efficient approach for accessing functionalized trisubstituted arylalkenes with amide groups. Herein, we report a rhodium‐catalyzed pyridylation of alkynamides with pyridylboronic acids, producing a variety of primary, secondary, and tertiary enamides with high yields (up to 94 %). This reaction demonstrates broad tolerance towards various alkyl and aryl functional groups, providing convenient access to a diverse array of alkenylpyridine derivatives. To demonstrate potential applications in late‐stage hydropyridylation, we synthesized α,β‐unsaturated ketones, aldehydes, and esters with high yields from the pyridylation product of Weinreb amides. This indirect expansion of the substrate scope enhances the practicality of this strategy. Additionally, the α,β‐unsaturated ketone obtained can be further reduced to yield a chiral alcohol with a 99 % ee, further demonstrating the versatility and potential utility of this approach. [ABSTRACT FROM AUTHOR]

A simple and mild protocol for the direct synthesis of vinyl nitriles is described. By employing potassium trimethylsilanolate as the mild base and benzyl chloride as the efficient promoter, a series of E‐configured vinyl nitriles are selectively obtained from readily available aldehydes and acetonitrile at room temperature without the aid of a transition metal catalyst. Mechanistical investigations reveal that this transformation may go through a Knoevenagel condensation process. [ABSTRACT FROM AUTHOR]

ABSTRACT Quinazolines and their derivatives occur in various natural products and pharmaceuticals, and thus, various methods of synthesizing quinazolines have been explored. They have traditionally been synthesized via two‐component reactions, but these strategies often suffer from the unavailability of the starting materials and limited substrate scopes. To overcome these problems, three‐component reactions using additional N sources were developed. Aldehydes were initially used in these reactions, but alcohols are greener and less toxic than aldehydes. However, the previously reported methods involving the use of alcohols require the utilization of transition metal catalysts, ultrahigh temperatures, and extended durations. Thus, an efficient, practical method of synthesizing quinazolines using alcohol is desirable. A facile one‐pot three‐component method of synthesizing quinazolines utilizing alcohols, 2‐aminobenzoketones, and ammonium acetate is reported for the first time, using active MnO2 and tert‐butyl hydrogen peroxide (TBHP) as synergistic oxidants. MnO2 and TBHP play dual roles: First, they oxidize the alcohol to the aldehyde and then facilitate the transformation of the intermediate into the product. During alcohol oxidation, the synergistic effect of MnO2 and TBHP is particularly evident. The aldehydes generated in situ via alcohol oxidation undergo immediate subsequent reactions, thereby minimizing their volatilization and side reactions, such as oxidation and polymerization. [ABSTRACT FROM AUTHOR]

Carbonyl addition serves as a strategically straightforward and versatile approach for synthesizing alcohols, which are often encountered within bioactive molecules. Herein, we present a ligand‐free, nickel‐catalyzed carbonyl addition process using organoboron reagents. This method enables efficient arylation of readily available ketones or aldehydes, affording a variety of tertiary and secondary alcohols. Key highlights of this protocol include the obviation of external ligands and the tolerance to many functional groups and heterocycles, thereby enhancing its practicality and utility in synthetic organic chemistry. [ABSTRACT FROM AUTHOR]

Rolling plays an important role in shaping the characteristic quality of black tea. However, the dynamic alterations in volatile compounds during the rolling process remain unclear, which hampers the quality control of black tea. In this study, the dynamic changes of volatile compounds in Congou black tea throughout the rolling process were explored by a combination of GC-E-Nose and GC-MS analysis. The results of PCA and PLS-DA by GC-E-Nose revealed significant alterations in the volatile profiles, particularly at the 15-min rolling stage. A total of 82 volatile compounds including eight categories were identified in Congou black tea during the rolling process. The most abundant volatiles were aldehydes, alcohols, and esters. Through the integration of variable importance in the projection >1 and p < 0.05, 21 volatile compounds were pinpointed as pivotal volatiles responsible for distinguishing diverse rolling processes. According to their pathways, glycoside-derived volatiles (GDVs) (such as linalool and geraniol) and fatty acid-derived volatiles (FADVs) (such as (Z)-2-hexen-1-ol and hexanal) highlighted the pivotal role in the formation of the aroma of black tea during rolling process. GDVs, characterized by floral, honeyed, and fruity aromas, reached the lowest point at 35-min rolling and subsequently rebounded. FADVs exhibited an ascending trajectory during the initial 15-min rolling, followed by a downward trend. These findings provide invaluable insights into the aroma evolution during the rolling stage, offering strategies for enhancing the aroma quality of Congou black tea. [ABSTRACT FROM AUTHOR]

The catalytic pyrolysis of guaiacol-based lignin monomers, vanillin, syringol, and eugenol over commercial HZSM-5 has been investigated using operando Photoelectron Photoion Coincidence (PEPICO) spectroscopy to unveil the reaction mechanism by detecting reactive intermediates, such as quinone methides and ketenes, and products. Vanillin shares the decomposition mechanism with guaiacol due to prompt and efficient decarbonylation, which allows us to control this reaction leading to a phenol selectivity increase by switching to a faujasite catalyst and decreasing the Si/Al ratio. Syringol first demethylates to 3-methoxycatechol, which mainly dehydroxylates to o- and m-guaiacol. Ketene formation channels over HZSM-5 are less important here than for guaiacol or vanillin, but product distribution remains similar. C3 addition to guaiacol yields eugenol, which shows a more complex product distribution upon catalytic pyrolysis. By analogies to monomers with simplified functionalization, namely allylbenzene, 4-allylcatechol, and 4-methylcatechol, the eugenol chemistry could be fully resolved. Previously postulated reactive semi-quinone intermediates are detected spectroscopically, and their involvement opens alternative pathways to condensation and phenol formation. Allyl groups, produced by dehydroxylation of the β-O-4 bond, may not only decompose via C1/C2/C3 loss, but also cyclize to indene and its derivatives over HZSM-5. This comparably high reactivity leads to an unselective branching of the chemistry and to a complex product distribution, which is difficult to control. Indenes and naphthalenes are also prototypical coke precursors efficiently deactivating the catalyst. We rely on these mechanistic insights to discuss strategies to fine-tune process conditions to increase the selectivities of desired products by enhancing either vanillin and guaiacol or supressing eugenol yields from native lignin. [ABSTRACT FROM AUTHOR]

Herein, we report an efficient route for coumarin C3‐C4 fused imidazole scaffolds via indium chloride‐mediated single‐step transformation of 4‐azido‐coumarin with amines/aldehydes and coumarin C3‐C4 fused 5‐substituted‐1,4‐benzodiazepine scaffolds with 1,2‐azide‐nitrogen migration through two‐step sequential synthesis via the transitory intermediacy of 2,3‐bridged‐2H‐azirine. A plausible mechanistic pathway has been proposed from the control/entrapment experiments and 1H‐NMR studies. This protocol provides the reaction condition‐dependent product selectivity, structural diversification, and excellent yields. [ABSTRACT FROM AUTHOR]

ABSTRACT The new type of the four‐component tandem Knoevenagel–Michael reaction was discovered: the transformation of arylaldehydes, N,N′‐dimethylbarbituric acid, malononitrile, and morpholine in alcohols and other organic solvents without any other additives at ambient temperature resulted in the selective formation of a new substituted unsymmetrical ionic scaffold with two pharmacology‐active heterocyclic rings. This new four‐component reaction is a simple and efficient route to a previously unknown substituted ionic unsymmetrical scaffold containing N,N′‐dimethylbarbituric acid and morpholine. These ionic scaffolds are promising for various biomedical applications, for example, as anticonvulsants and anti‐inflammatory drugs, as well as anti‐AIDS agents. In this research, we also accomplished the efficient cyclization of morpholin‐4‐ium 5‐(2,2‐dicya‐no‐1‐arylethyl)‐1,3‐dimethyl‐2,6‐di‐oxo‐1,2,3,6‐tetrahydro‐pyrimidin‐4‐olates by the action of NBS–NaOAc system, with the formation of 5,7‐dimethyl‐4,6,8‐trioxo‐2‐aryl‐5,7‐diazaspiro[2.5]octane‐1,1‐dicarbonitriles in 83%–98% yields. In the final stage of our research, direct one‐pot multicomponent transformation of benzaldehydes, N,N′‐dimethylbarbituric acid, and malononitrile into spirobarbituric cyclopropanes was accomplished in 75%–97% yields. The spiro‐barbituric cyclopropanes are potentially active as remedies against various inflammatory, infectious, immunological, or malignant diseases. [ABSTRACT FROM AUTHOR]

We report an efficient protocol for oxidation of primary/secondary benzyl alcohols and benzylamines to produce corresponding aldehydes or ketones. Our unified method involves the use of commercially available (diethylamino)sulfur trifluoride (DAST) as a reagent combined with DMSO as solvent and oxidant. The reaction provided corresponding carbonyl compounds in good to excellent yields with high purity and in short reaction times. [ABSTRACT FROM AUTHOR]

Comprehensive Summary: Transition‐metal‐catalyzed asymmetric alkylation of aldehydes represents a straightforward strategy for the synthesis of chiral secondary alcohols. However, efficient methods using organoborons as coupling reagents are rare. Herein, we report a highly enantioselective nickel‐catalyzed alkylation reaction of aldehydes, using readily available alkylborons as nucleophiles. A wide variety of chiral secondary alcohols were prepared from commercially available aldehydes with high yields. The key to the excellent enantioselectivity and chemoselectivity was the employment of a bulky C2‐symmetric chiral NHC ligand. This protocol features excellent enantiocontrol, mild conditions, and good functional group compatibility. [ABSTRACT FROM AUTHOR]

As an in‐depth profile control agent, water‐soluble phenolic resin crosslinking polyacrylamide weak gel has been widely used in the middle and high water cut stage of water flooding reservoir. In this study, the phenolic resin was synthesized by two‐step alkali catalysis. Factors influencing the synthesis of phenolic resin, including the molar ratio of phenol and formaldehyde, catalyst types, reaction time, were investigated with hydroxylmethyl and aldehyde content as the criterion. When the molar ratio of phenolic resin was 1:2 and NaOH was catalyst, at 80°C for 4 h, the phenolic resin had the highest hydroxymethyl content (49.37%) and the lowest free aldehyde content (2.95%). Weak gel was formed by the reaction of LT002‐polyacrylamide with phenolic resin. Taking the gelation time and strength as criteria, the factors influencing the crosslinking property, including hydroxymethyl content, crosslinker addition, and polyacrylamide concentration were investigated respectively. Under optimal formulation, the property investigation shows that the hydroxymethyl group in the phenolic resin can be crosslinked with the amide group in polyacrylamide, the gelation time is long (50–60 h), and the gelation strength is larger than 5 × 104 mPa s, which is conductive to the plugging of deep oil layers. When the permeability was 5061 × 10−3 μm2, the plugging rate was 72.73%. [ABSTRACT FROM AUTHOR]

Copyright of Science & Technology of Food Industry is the property of Science & Technology of Food Industry Editorial Office and its content may not be copied or emailed to multiple sites or posted to a listserv without the copyright holder's express written permission. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)

Comprehensive Summary: Transition‐metal‐catalyzed asymmetric alkylation of aldehydes represents a straightforward strategy for the synthesis of chiral secondary alcohols. However, efficient methods using organoborons as coupling reagents are rare. Herein, we report a highly enantioselective nickel‐catalyzed alkylation reaction of aldehydes, using readily available alkylborons as nucleophiles. A wide variety of chiral secondary alcohols were prepared from commercially available aldehydes with high yields. The key to the excellent enantioselectivity and chemoselectivity was the employment of a bulky C2‐symmetric chiral NHC ligand. This protocol features excellent enantiocontrol, mild conditions, and good functional group compatibility. [ABSTRACT FROM AUTHOR]

Herein, we unveil a novel electrochemical oxidative strategy that facilitates the synthesis of lactones from 2‐arylbenzaldehydes and 2‐arylbenzoic acids. Crucially, our method allows for the convergent synthesis of lactones from the combinations of the respective 2‐arylbenzaldehyde and 2‐arylbenzoic acid as starting material, owing to the oxidative process's compatibility within our electrochemical setup. This approach offers a robust and versatile pathway to construct various dibenzopyranones type lactone compounds through an environmentally considerate and economically advantageous process. [ABSTRACT FROM AUTHOR]

Chromene derivatives are important oxygen heterocycles, which are met in numerous natural products, pharmaceuticals, and organic functional materials. This review survey the achievements in the synthesis of chromene derivatives from α,β‐unsaturated aldehydes. Particular attention is paid to the use of catalytic systems, synthetic advantages and mechanistic aspects of the reactions. The works published over the past 15 years are covered. [ABSTRACT FROM AUTHOR]

A one-step, on-tissue chemical derivatisation method for MALDI mass spectrometry imaging was found to improve the detectability of aldehydes and ketones by charge-tagging. The developed reactive matrices, containing a UV-chromophore, ionisable moiety and hydrazide group, showed an equal or higher detection efficiency than Girard's reagent P, enabling improved imaging of brain metabolites without the need for additional co-matrices. [ABSTRACT FROM AUTHOR]

The facile generation of the α‐acyloxy carboxamide radical is hereby reported for the first time, utilizing a photoredox catalyzed reaction of Passerini adducts synthesized using a 4‐formyl‐1,4‐dihydropyridine as the carbonyl component. This radical effectively engages in a Giese reaction with a range of olefins, ultimately leading to the synthesis of novel Passerini‐derived products not previously amenable to direct aldehyde‐based transformations. Consequently, the resulting strategy, developed both in batch and in flow, offers a promising opportunity to expand the chemical space accessible through the Passerini reaction, virtually incorporating "impossible" aldehydes. [ABSTRACT FROM AUTHOR]

The Petasis reaction is a multicomponent reaction of aldehydes, amines and organoboron reagents and is a useful method for the construction of substituted amines. Despite the significant advancement of the Petasis reaction since its invention in 1993, strategies for asymmetric and non‐directed Petasis reactions remain limited. To date, there are very few catalytic asymmetric Petasis reactions and almost all asymmetric reports employ a chiral auxiliary. Likewise, the aldehyde component often requires a directing group, ultimately limiting the reaction's scope. In this Concept, key methods for asymmetric and non‐directed Petasis reactions are discussed, focusing on how these conceptual advances can be applied to solve long‐standing gaps in the Petasis literature. [ABSTRACT FROM AUTHOR]

The aerobic oxidation of dibenzothiophene (DBT) was studied in hexadecane under ultrasonic treatment. Under these conditions, aldehydes can activate oxygen; however, the activation efficiency largely depends on the chemical nature of the aldehyde. The time dependence of the DBT oxidation in hexadecane was studied in the presence of valeraldehyde, caprinaldehyde, benzaldehyde, and anisaldehyde. After the treatment, the DBT concentration in hexadecane can decrease from 100 to 6 ppm. In the absence of ultrasonic treatment, the reaction does not proceed under these conditions. [ABSTRACT FROM AUTHOR]

The literature data on the use of triphenylphosphine in determining peroxide functional groups and individual oxygen-containing compounds in the composition of the products of oxidation reactions of organic compounds with molecular oxygen and/or peroxides were systematized and discussed. The causes and mechanisms of distortions of the results of analytical determinations were identified and possible ways of their elimination were suggested. [ABSTRACT FROM AUTHOR]

It is a fluorescence-based study to examine the interaction between L-tryptophan and a selection of aldehydes, namely furfural (furan-2-carbaldehyde), 3-hydroxybenzaldehyde, salicylaldehyde (2-hydroxybenzaldehyde), 3-nitrobenzaldehyde, and 4-bromobenzaldehyde. The investigation took place in an aqueous environment, revealing that all five aldehydes induced quenching of the fluorescence intensity of L-tryptophan. By employing the Stern-Volmer equation to describe the quenching process, we constructed Stern-Volmer plots and derived Stern-Volmer constants. These constants (KSV) ranged from 2.87 × 104 mol L− 1 to 5.75 × 104 mol L− 1. Notably, the values of the Stern-Volmer constants varied among the different aldehydes, with the following order: 3-hydroxybenzaldehyde(3-HBA) > 4-bromobenzaldehyde (4-BBA) > 3-nitrobenzaldehyde > furan-2-carbaldehyde > salicylaldehyde. Consequently, our findings highlighted 3-hydroxybenzaldehyde as the most potent quencher, while 2-hydroxybenzaldehyde displayed the least sensitivity to quenching. Additionally, we determined the detection and quantification limits for the investigated aldehydes, resulting in ranges of 3.87 × 10− 12 to 8.25 × 10− 6 and 1.29 × 10− 11 to 2.75 × 10− 5, respectively. This research paves the way for the development of novel fluorescence probe-based sensors and offers valuable techniques for analyzing aldehydes within environmental and biological samples. [ABSTRACT FROM AUTHOR]

Tunable hydrogels have gained significant attention in the bioengineering field due to their designer preparation approach. Towards this end, gelatine stands out as a promising candidate owing to its desirable attributes, such as biocompatibility, ability to support cell adhesion and proliferation, biodegradability, and cost-effectiveness. This study presents the preparation of a robust gelatine hydrogel employing sacran aldehyde (SDA) as a natural cross-linker. The resulting SDA-cross-linked gelatine hydrogels (GSDA) display an optimal compressive stress of 0.15 MPa at 50% strain, five times higher than pure gelatine hydrogel. As SDA cross-linking concentration is increased, the swelling capacity of GSDA declines. This decline in swelling capacity, from 80% to 40%, is a result of strong crosslinking of gelatin with SDA. Probing further with FT-IR spectroscopy and SEM at the micron scale unveiled a dual-cross-linking mechanism within the hydrogels. This mechanism encompasses both short- and long-range covalent cross-linking, along with thermo-induced physical cross-linking, resulting in a significant enhancement of the load-bearing capacity of the fabricated hydrogels. [ABSTRACT FROM AUTHOR]

In this study, 13 different edible weed species [Centaurea depressa Bieb., Cichorium intybus L., Lactuca serriola L., Malva neglecta Wallr., Papaver dubium L., Polygonum cognatum Meissn., Rumex patientia L., Scorzonera cana (C.A.Mey.Hoffm.), Silene alba (Mill.) Krause, Stellaria media L., Sonchus oleraceus L., Taraxacum officinale, Tragopogon longirostris Bisch] were collected from the same location in the Mediterranean region. Then, the leaves of all species were analyzed by the SPME-GC/MS method for the detection of volatile compounds. The compounds were grouped according to their structures as alcohols, aldehydes, alkanes, ester, furans, hydrocarbons, ketones, sulfur compounds, and terpenes. The percentages of the terpenes, aldehydes and alcoholic compounds were found to have the highest ratios of volatile compounds, respectively. The species found with the highest total terpene percentage was Sonchus oleraceus L. (78.84%), while the lowest one was Stellaria media L. (51.03%). Similarly, the highest total aldehydes percentage was found in Stellaria media L. (38.41%), and the lowest was in Centaurea depressa Bieb. (4.62%). Lastly, the highest total alcohol percentage was observed in Centaurea depressa Bieb. (9.92%) and the lowest was in Malva neglecta Wallr. (1.11%). The limonene, which is an important monoterpene, among 63 components, was found to be the major component in all species with a range of approximately 51-79%. Among them, Sonchus oleraceus L. had the highest limonene content (78.84%). [ABSTRACT FROM AUTHOR]

A new eco-friendly method for the synthesis of mono- and multifunctional organosulfur compounds, based on the process between ynals and thiols, catalyzed by bulky N-heterocyclic carbene (NHC), was designed and optimized. The proposed organocatalytic approach allows the straightforward formation of a broad range of thioesters and sulfenyl-substituted aldehydes in yields above 86%, in mild and metal-free conditions. In this study, thirty-six sulfur-based derivatives were obtained and characterized by spectroscopic methods. [ABSTRACT FROM AUTHOR]

Cyano and amide are important functionalities in medicinal chemistry, and organic chemistry transformations. We have devised a new, safe, and easy method for the synthesis of cyano and further amide using aldehyde via copper-mediated cyanation and amidation with ammonium acetate/iodine in DMF in a time-dependent manner. This approach efficiently converts aryl/alkyl/hetero aldehydes into their corresponding cyano which can be isolated after 3 h and/or if continued for 24 h then in-situ transformed into amide derivatives. Herein cupric acetate plays the role of coordinator, ammonium acetate is the nitrogen source, while DMF serves as a carbon source. We did easy and safe cyanation to explore the synthesis of varieties of cyano in 69–86% yields and respective amide derivatives in 58–75% yields. Thus, this process can serve the dual advantage in the synthesis of cyano and amides bioactive scaffold using respective aldehyde. [ABSTRACT FROM AUTHOR]

Objective: The objective of this study is to determine the associations of protein‐specific anti–malondialdehyde‐acetaldehyde (MAA) antibodies with prevalent and incident rheumatoid arthritis–interstitial lung disease (RA‐ILD). Methods: Within a multicenter, prospective cohort of US veterans with RA, RA‐ILD was validated by medical record review of clinical diagnoses, chest imaging, and pathology. Serum antibodies to MAA‐albumin, MAA‐collagen, MAA‐fibrinogen, and MAA‐vimentin (IgA, IgM, and IgG) were measured by a standardized enzyme‐linked immunosorbent assay. Associations of anti‐MAA antibodies with prevalent and incident RA‐ILD were assessed using multivariable regression models adjusting for established RA‐ILD risk factors. Results: Among 2,739 participants with RA (88% male, mean age of 64 years), there were 114 with prevalent and 136 with incident RA‐ILD (average time to diagnosis: 6.6 years). Higher IgM anti–MAA‐collagen (per 1 SD: adjusted odds ratio [aOR] 1.28, 95% confidence interval [CI] 1.02–1.61), IgA anti–MAA‐fibrinogen (aOR 1.48, 95% CI 1.14–1.92), and IgA (aOR 1.78, 95% CI 1.34–2.37) and IgG (aOR 1.48, 95% CI 1.14–1.92) anti–MAA‐vimentin antibodies were associated with prevalent RA‐ILD. In incident analyses, higher IgA (per one SD: adjusted hazards ratio [aHR] 1.40, 95% CI 1.11–1.76) and IgM (aHR 1.29, 95% CI 1.04–1.60) anti–MAA‐albumin antibody concentrations were associated with increased ILD risk. Participants with IgA (aHR 2.13, 95% CI 1.16–3.90) or IgM (aHR 1.98, 95% CI 1.08–3.64) anti–MAA‐albumin antibody concentrations in the highest quartile had an approximately two‐fold increased risk of incident RA‐ILD. Across all isotypes, anti–MAA‐fibrinogen, anti–MAA‐collagen, and anti–MAA‐vimentin antibodies were not significantly associated with incident RA‐ILD. Conclusion: Protein‐specific anti‐MAA antibodies to collagen, fibrinogen, and vimentin were associated with prevalent RA‐ILD. IgA and IgM anti–MAA‐albumin antibodies were associated with a higher risk of incident RA‐ILD. These findings suggest that MAA modifications and resultant immune responses may contribute to RA‐ILD pathogenesis. [ABSTRACT FROM AUTHOR]

Summary: This study investigated the effects of reducing sugars and protein‐to‐sugar ratios on generating volatile compounds from nutritional yeast hydrolysates after Maillard reaction. Nutritional yeast extract (NYE) was cleaved using Flavourzyme® at an enzyme‐to‐substrate ratio of 0.5% w/w, followed by heat treatment with varying concentrations of reducing sugars (i.e., hexoses: glucose and fructose and pentoses: xylose and ribose). The results showed that pentoses generate higher numbers and concentrations of volatiles than hexoses, especially furans, Strecker aldehydes, and sulphur‐containing compounds such as dimethyl disulphide. However, hexoses produced higher concentrations of pyrazines. Strecker aldehydes and pyrazines served as key aroma‐active compounds in meat aroma. Likewise, sulphur‐containing compounds played an important role in meat aroma due to their low detection threshold. The results showed that reducing sugars significantly impacts the volatile profile of NYE, potentially influencing the formation of meaty aroma compounds. These findings demonstrate the potential of MRPs to enhance meaty flavours due to the presence of volatile compounds with characteristics of cooked meat. [ABSTRACT FROM AUTHOR]

Simple, environmentally benign and metal free one pot strategy has been used for the synthesis of 4-iodo-3-phenylbenzo[b][1,6]naphthyridine from O-alkynylquinolinyl aldehydes with tert-butyl amine and iodine through imine formation in good to excellent yield at room temperature in aerobic and mild conditions. The beauty of this reaction is the imine formation and cyclization in the same reaction pot. Due to presence of iodine in product, it can be useful for further reaction and can be valuable synthon for new organic compounds. [ABSTRACT FROM AUTHOR]

Hierarchical Co3O4/triple-shelled carbon nitride (Co3O4/TSCN) composite nanocapsules were designed via a multi-step procedure in a controlled manner as a solar-light-driven photocatalyst based Z-scheme system for selective aerobic photooxidation of alcohols (primary and secondary aliphatic and benzylic) to corresponding aldehydes/ or ketones in green media. The structure of the as-prepared photocatalyst was characterized by a series of measurement techniques including FT-IR, XRD, BET, TEM, FE-SEM, EDX, EDX-mapping, TGA, UV–vis DRS, and ICP-OES. The hierarchical Co3O4/TSCN composite nanocapsules demonstrated superior photocatalytic activity in selective aerobic oxidation of alcohols under solar light irradiation in comparison to pure TSCN and Co3O4 NPs. The shell number of the composite nanocapsules and the formation of the hierarchical Co3O4/TSCN Z-scheme photocatalyst can significantly affect the photocatalytic activity. The results indicate the efficient electron transfer, relatively high specific surface area, high donor density, and low band gap as well as the coexistence of micro-, meso- and macropores and also nano-sized crystalline structure (from 1.2 to 95 nm) in heterojunction composite. This novel photocatalytic system kept relatively high catalytic activity after five recycle runs under the same reaction conditions. [ABSTRACT FROM AUTHOR]

To mitigate the losses due to fall armyworm (FAW) infestation in maize, chemical pesticides had been the first choice and widely used as an emergency response. However, it comes with attendant health effect. This necessitates the development of plant based effective and safer pesticides. This research investigate response of fall armyworm larvae when they are exposed to crude and partially purified Tithonia diversifolia leaf extract. Chemical constituent of the extract was identified using NIST08.LIB library spectra provided by the software on a GC-MS system and FTIR analysis was done using KBr pellet technique with a resolution and scanning speed of 4 cm−1 and 2 mm/s. Dose dependent toxicity assay of T. diversifolia extracts on FAW at different growth stages under controlled environment in laboratory, followed by its effect under phytotron were examined against control and azadirachtin from neem. The GC-MS of the butanol eluent revealed 20 compounds out of which the major ones being beta-d-glucopyranoside, methyl (15.225 %) palmitic acid, TMS derivative (10.98 %) and hexadecanoic acid, 2-[(trimethylsily)oxy]-, methyl ester (8.75 %). The FT-IR spectroscopic analysis of the butanol eluent of T. diversifolia leaf extract revealed the presence of alcohols, phenols, aldehydes, ketones, alkanes and primary amines. The butanol eluent and crude extract caused 96 % mortality at neonate and first instar FAW larvae. The toxic and repellant effects revealed by diet bioassay and phytotron experiment respectively suggest that butanol eluent of T. diversifolia leaf extract could be a good and effective target for biopesticide production against FAW. [ABSTRACT FROM AUTHOR]

Overdose of acetaminophen (APAP) produces fulminant hepatic necrosis. The underlying mechanism of APAP hepatotoxicity involves mitochondrial dysfunction, including mitochondrial oxidant stress and the onset of mitochondrial permeability transition (MPT). Reactive oxygen species (ROS) play an important role in APAP-induced hepatotoxicity, and iron is a critical catalyst for ROS formation. This review summarizes the role of mitochondrial ROS formation in APAP hepatotoxicity and further focuses on the role of iron. Normally, hepatocytes take up Fe3+-transferrin bound to transferrin receptors via endocytosis. Concentrated into lysosomes, the controlled release of iron is required for the mitochondrial biosynthesis of heme and non-heme iron-sulfur clusters. After APAP overdose, the toxic metabolite, NAPQI, damages lysosomes, causing excess iron release and the mitochondrial uptake of Fe2+ by the mitochondrial calcium uniporter (MCU). NAPQI also inhibits mitochondrial respiration to promote ROS formation, including H2O2, with which Fe2+ reacts to form highly reactive •OH through the Fenton reaction. •OH, in turn, causes lipid peroxidation, the formation of toxic aldehydes, induction of the MPT, and ultimately, cell death. Fe2+ also facilitates protein nitration. Targeting pathways of mitochondrial iron movement and consequent iron-dependent mitochondrial ROS formation is a promising strategy to intervene against APAP hepatotoxicity in a clinical setting. [ABSTRACT FROM AUTHOR]

Photoinduced chemical reactions and the development of new materials represent a current and significant topic. We present a sustainable and eco-friendly approach to the Knoevenagel condensation reaction involving carbonyl and active methylene compounds. Our method utilizes photo-activated carbon dots (CDs) derived from 5-hydroxymethylfurfural (5HMF) within an aqueous medium and does not require acidic, basic, or thermal conditions. This protocol operates effectively with aromatic, aliphatic, and heteroaromatic aldehydes and ketones. The 5HMF-derived-CDs can be reused four times without significant loss of activity. Moreover, this methodology is suitable for scaling up reactions, thereby highlighting its potential for industrial applications. [ABSTRACT FROM AUTHOR]

The enantiodivergent synthesis of syn‐Michael adducts can be easily achieved by switching the terminal proline in dipeptidic proline‐thiourea catalysts. In this study, a dipeptidic proline‐derived thiourea organocatalyst was rationally designed and facilely prepared from dipeptidic proline, a chiral diamine as a linker, and isothiocyanate. This asymmetric bifunctional catalyst for Michael addition between aldehydes and nitroolefins provided chiral 4‐nitro aldehyde adducts with yields of up to 99 %, 92 : 8 syn‐diastereoselectivity, and 97 % enantiomeric excess at room temperature. [ABSTRACT FROM AUTHOR]