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Determining the structure and phenotypic context of molecules detected in untargeted metabolomics experiments remains challenging. Here we present reverse metabolomics as a discovery strategy, whereby tandem mass spectrometry spectra acquired from newly synthesized compounds are searched for in public metabolomics datasets to uncover phenotypic associations. To demonstrate the concept, we broadly synthesized and explored multiple classes of metabolites in humans, including N-acyl amides, fatty acid esters of hydroxy fatty acids, bile acid esters and conjugated bile acids. Using repository-scale analysis1,2, we discovered that some conjugated bile acids are associated with inflammatory bowel disease (IBD). Validation using four distinct human IBD cohorts showed that cholic acids conjugated to Glu, Ile/Leu, Phe, Thr, Trp or Tyr are increased in Crohn's disease. Several of these compounds and related structures affected pathways associated with IBD, such as interferon-γ production in CD4+ T cells3 and agonism of the pregnane X receptor4. Culture of bacteria belonging to the Bifidobacterium, Clostridium and Enterococcus genera produced these bile amidates. Because searching repositories with tandem mass spectrometry spectra has only recently become possible, this reverse metabolomics approach can now be used as a general strategy to discover other molecules from human and animal ecosystems.

BackgroundWidespread exposure to organophosphate ester (OPE) flame retardants with potential reproductive toxicity raises concern regarding the impacts of gestational exposure on birth outcomes. Previous studies of prenatal OPE exposure and birth outcomes had limited sample sizes, with inconclusive results.ObjectivesWe conducted a collaborative analysis of associations between gestational OPE exposures and adverse birth outcomes and tested whether associations were modified by sex.MethodsWe included 6,646 pregnant participants from 16 cohorts in the Environmental influences on Child Health Outcomes (ECHO) Program. Nine OPE biomarkers were quantified in maternal urine samples collected primarily during the second and third trimester and modeled as log2-transformed continuous, categorized (high/low/nondetect), or dichotomous (detect/nondetect) variables depending on detection frequency. We used covariate-adjusted linear, logistic, and multinomial regression with generalized estimating equations, accounting for cohort-level clustering, to estimate associations of OPE biomarkers with gestational length and birth weight outcomes. Secondarily, we assessed effect modification by sex.ResultsThree OPE biomarkers [diphenyl phosphate (DPHP), a composite of dibutyl phosphate and di-isobutyl phosphate (DBUP/DIBP), and bis(1,3-dichloro-2-propyl) phosphate] were detected in >85% of participants. In adjusted models, DBUP/DIBP [odds ratio (OR) per doubling=1.07; 95% confidence interval (CI): 1.02, 1.12] and bis(butoxyethyl) phosphate (OR for high vs. nondetect=1.25; 95% CI: 1.06, 1.46), but not other OPE biomarkers, were associated with higher odds of preterm birth. We observed effect modification by sex for associations of DPHP and high bis(2-chloroethyl) phosphate with completed gestational weeks and odds of preterm birth, with adverse associations among females. In addition, newborns of mothers with detectable bis(1-chloro-2-propyl) phosphate, bis(2-methylphenyl) phosphate, and dipropyl phosphate had higher birth weight-for-gestational-age z-scores (β for detect vs. nondetect=0.04-0.07); other chemicals showed null associations.DiscussionIn the largest study to date, we find gestational exposures to several OPEs are associated with earlier timing of birth, especially among female neonates, or with greater fetal growth. https://doi.org/10.1289/EHP13182.

We present a theoretical investigation on the esterification process for boron ester synthesis, considering boric acid and 2(R),4(S)-pentanediol as model boron and diol derivatives, respectively. We report an unprecedented mechanistic pathway, able to rationalise, in contrast with the reported ones, the relatively low Gibbs energies of activation and the pH dependence experimentally observed in the formation of boron esters. We believe that these findings will improve the possibility to predict cross-link reaction rates of boron esters as a fundamental tool in the rational design of functional materials based on boron–oxygen linkages. [ABSTRACT FROM AUTHOR]

The first dispiro orthoester via a spiroacetal oxo-carbenium ion is presented. Oxidative dearomatization of phloretic esters results in a bifunctional electrophilic spiroacetal oxo-carbenium ion, which undergoes a double nucleophilic addition by diol delivering a range of unusual dispiro-orthoesters with an excellent diversity. [ABSTRACT FROM AUTHOR]

Comprehensive Summary The EDA complex‐mediated reactions involving oxime esters have been few studied. Herein, an EDA complex formed by thiophenolate anion and oxime ester is reported for photoinduced divergent synthesis of thioethers, depending on different types of oxime esters. Operational simplicity, mild reaction conditions, and flexible options of leaving group demonstrate the generality and synthetic utility of this approach. Such an approach can also enable an interesting thiol‐catalysis for the synthesis of phenanthridines. [ABSTRACT FROM AUTHOR]

BACKGROUND: Heart failure with preserved ejection fraction (HFpEF) is a major cause of morbidity and mortality in patients with type 2 diabetes (T2D). Acute increases in circulating levels of ketone body 3-hydroxybutyrate have beneficial acute hemodynamic effects in patients without T2D with chronic heart failure with reduced ejection fraction. However, the cardiovascular effects of prolonged oral ketone ester (KE) treatment in patients with T2D and HFpEF remain unknown. METHODS: A total of 24 patients with T2D and HFpEF completed a 6-week randomized, double-blind crossover study. All patients received 2 weeks of KE treatment (25 g D-ß-hydroxybutyrate-(R)-1,3-butanediol × 4 daily) and isocaloric and isovolumic placebo, separated by a 2-week washout period. At the end of each treatment period, patients underwent right heart catheterization, echocardiography, and blood samples at trough levels of intervention, and then during a 4-hour resting period after a single dose. A subsequent second dose was administered, followed by an exercise test. The primary end point was cardiac output during the 4-hour rest period. RESULTS: During the 4-hour resting period, circulating 3-hydroxybutyrate levels were 10-fold higher after KE treatment (1010±56 μmol/L; P<0.001) compared with placebo (91±55 μmol/L). Compared with placebo, KE treatment increased cardiac output by 0.2 L/min (95% CI, 0.1 to 0.3) during the 4-hour period and decreased pulmonary capillary wedge pressure at rest by 1 mm Hg (95% CI, -2 to 0) and at peak exercise by 5 mm Hg (95% CI, -9 to -1). KE treatment decreased the pressure-flow relationship (Δ pulmonary capillary wedge pressure/Δ cardiac output) significantly during exercise (P<0.001) and increased stroke volume by 10 mL (95% CI, 0 to 20) at peak exercise. KE right-shifted the left ventricular end-diastolic pressure-volume relationship, suggestive of reduced left ventricular stiffness and improved compliance. Favorable hemodynamic responses of KE treatment were also observed in patients treated with sodium-glucose transporter-2 inhibitors and glucagon-like peptide-1 analogs. CONCLUSIONS: In patients with T2D and HFpEF, a 2-week oral KE treatment increased cardiac output and reduced cardiac filling pressures and ventricular stiffness. At peak exercise, KE treatment markedly decreased pulmonary capillary wedge pressure and improved pressure-flow relationship. Modulation of circulating ketone levels is a potential new treatment modality for patients with T2D and HFpEF. [ABSTRACT FROM AUTHOR]

Comprehensive Summary The EDA complex‐mediated reactions involving oxime esters have been few studied. Herein, an EDA complex formed by thiophenolate anion and oxime ester is reported for photoinduced divergent synthesis of thioethers, depending on different types of oxime esters. Operational simplicity, mild reaction conditions, and flexible options of leaving group demonstrate the generality and synthetic utility of this approach. Such an approach can also enable an interesting thiol‐catalysis for the synthesis of phenanthridines. [ABSTRACT FROM AUTHOR]

Bis‐dioxolene ligands 1–5, linked by m‐dioxyarylene spacers were synthesized. Such ligands are considered as potential building blocks for coordination‐driven design of cage‐like units by self‐assembly mechanism. The peculiarity of new species is in presence of additional functional group in the linker such as pyridinyl (1), ester (2–3), and carboxyl (4–5) that add the possibilities for ordering modes during the design of coordination polymers. Di‐o‐quinones 1–2 were synthesized by reaction of 4‐chloro‐3,6‐di‐tert‐butyl‐o‐quinone (4‐Cl‐3,6‐Q) with pyridine‐3,5‐diol and methyl 3,5‐dixydroxybenzoate, respectively, in presence of base. The preparation of di‐o‐quinone 5 turned to be a multistage process where di‐catechols 3–4 were isolated as intermediates. [ABSTRACT FROM AUTHOR]

The irreversible locking of reversible imine linkages in COFs into quinoline-4-carboxylic esters has been achieved for the first time through the Doebner–von Miller reaction. The high conversion efficiency and broad scope were demonstrated by synthesizing four quinoline-4-carboxylic ester-linked COFs (QCE-COFs). Subsequently, this approach was applied to create the chiral QCE-COF-Men containing L -menthol. Remarkably, QCE-COF-Men was found to release the flavorant L -menthol at elevated temperature by cleaving the weak ester bond without destroying the quinoline skeleton. [ABSTRACT FROM AUTHOR]

Tf2NH‐mediated decarboxylative dearomatization reaction of benzonorcaradiene γ‐ketoacids, in situ generated by intramolecular alkenylation of alkynylcyclopropane γ‐ketoacids or their tert‐butyl esters, has been described for regioselective synthesis of polyfunctionalized 1‐acylmethyl‐4‐arylnaphthalenes. [ABSTRACT FROM AUTHOR]

Herein, we report an efficient strategy towards the synthesis of amino acid substituted isoquinoline derivatives via reaction of unprotected amino acid/amino acid ester/amino acid based drugs with 2‐(2‐oxo‐2‐aryl/alkylethyl)benzonitrile under metal‐free conditions. The developed protocol is highly simple and shows functional group tolerance to provide corresponding novel amino acid substituted isoquinolines in aqueous medium. The applicability of the reaction is an easier modification of well‐known drugs and successfully extended to gram‐scale synthesis. [ABSTRACT FROM AUTHOR]

Protected lysine esters (Boc‐L‐Lys(Boc)‐OSu) an intermediate of high repute in the peptide synthesis and diverse chemical synthetic applications, was the subject of synthetic process development studies, unveiling process‐related impurities. These impurities were synthesized, characterized, and identified by different analytical tools, with their retention times verified by HPLC co‐injection with commercial products. Detailed discussions ensued on the potential formation pathways and synthetic strategies of these process‐related impurities. [ABSTRACT FROM AUTHOR]

The article discusses the synthesis of aryl benzothiazole derivatives using microwave-assisted phase transfer catalysis, highlighting their potential as anticancer agents. Various synthetic methods and reactions are explored, with a focus on optimizing reaction conditions for high yields. The synthesized compounds are tested for anticancer activity against different cancer cell lines, showing promising results. The study aims to provide a convenient method for preparing aryl benzothiazoles and stimulate further research into their anticancer potential. [Extracted from the article]

A simple and efficient three‐component coupling reaction of carboxylic acids, diazo compounds, and tertiary amines catalyzed by manganese has been described. This reaction proceeds smoothly under mild conditions to afford various β‐amino esters in moderate to good yields by using O2 as the terminal oxidant. In this process, Mn‐based carbene radical, single‐electron transfer, and nucleophilic attack were fused into a reaction system. [ABSTRACT FROM AUTHOR]

Data on the occurrence of organophosphate tri-esters (tri-OPEs) and their metabolites (di-OPEs) in hen’s eggs are scarce. Therefore, 200 egg samples were gathered in 2023 in Hanoi, Vietnam and analysed by UHPLC-Q-Exactive HRMS. The majority of these compounds were detected, with tris(2-ethylhexyl) phosphate (0.10–2.7 ng/g wet weight (ww)) and trihexyl phosphate (0.08–2.3 ng/g ww) being the most prevalent tri-OPEs. Significant differences in tri-OPE profiles were observed in egg samples from battery-cage and free-range farming (p < .05). Despite egg levels ranging from 0.05 to 11.2 ng/g ww, Σdi-OPE accumulation in yolk and egg white was not significantly different in (p > .05). Among di-OPEs, dibutyl phosphate was found at the highest levels in the egg white, while bis(2-ethylhexyl) phosphate had the highest levels in yolk. There was no carcinogenic human health risk associated with OPEs in eggs (HQs <1). [ABSTRACT FROM AUTHOR]

Introduction: Skin greasiness occurred on stored apples (Malus domestica Borkh.) is generally believed to result from changes in surface wax components. Previous reports have typically correlated wax changes with greasiness scores to reveal the contributing wax components. A notable limitation of this approach is that greasiness scores are highly subjective and influenced by individual perception. Methods: This study aimed to assess skin quality by quantitatively analyzing wax morphology changes in greasy ‘Jonagold’ apples using Atomic Force Microscopy (AFM) roughness parameters Ra, Rq, Rmax, and Rz, and to correlate these changes with wax composition. Results: AFM results revealed that wax crystals disappeared as skin greasiness increased, accompanied by significant declines in roughness parameters Ra, Rq, Rmax, and Rz, which decreased by 70% to 85%. Chemical analysis showed a significant increase in liquid esters, including linoleate and oleate esters, in the surface waxes, which negatively correlated with the decline in roughness parameters. Key genes related to ester production, such as MdFAD2, MdWSD1, and MdWBC11, exhibited increased expression and were also negatively correlated with decreases in Rq, Ra and Rz. Additionally, 1-Methylcyclopropene (1-MCP) treatment suppressed both the development of greasiness and the associated changes. Discussion: Our findings suggest that the increased liquid esters contribute to alternations in wax morphology in greasy apples, and that MdFAD2, MdWSD1, and MdWBC11, play crucial roles in ester biosynthesis. These results highlight the effectiveness of AFM roughness parameters Ra, Rq, Rmax, and Rz in quantifying wax morphology changes in apples during skin greasiness development. [ABSTRACT FROM AUTHOR]

Interactions between lone pairs and aromatic π systems are significant across biology and self‐assembled materials. Herein, employing an achiral confinement metal–organic framework (MOF) encapsulates guest molecules, it is successfully realized that lone pair (lp)‐π interaction induces fluorescence "turn‐on" and circularly polarized luminescence for the first time. The MOFs synthesized based on naphthalenediimide show nearly non‐emissive, which can be light‐up by introducing acetone or ester guests containing lone pairs‐π interaction. Furthermore, the introduction of a series of lp‐rich chiral esters induces supramolecular chirality as well as circularly polarized luminescence in achiral MOFs, while also observing chiral adaptability. This work first demonstrates the luminescence and chiral induction via lone pair electrons‐π interactions, presenting a fresh paradigm for the advancement of chiroptical materials. [ABSTRACT FROM AUTHOR]

The Yamaguchi reagent, based on 2,4,6-trichlorobenzoyl chloride (TCBC) and 4-dimethylaminopyridine (DMAP), is an efficient tool for conducting the intermolecular (esterification) reaction between an acid and an alcohol in the presence of a suitable base (Et3N or iPr2NEt) and solvent (THF, DCM, or toluene). The Yamaguchi protocol is renowned for its ability to efficiently produce a diverse array of functionalized esters, promoting high yields, regioselectivity, and easy handling under mild conditions with short reaction times. Here, the recent utilization of the Yamaguchi reagent was reviewed in the synthesis of various natural products such as macrolides, terpenoids, polyketides, peptides, and metabolites. [ABSTRACT FROM AUTHOR]

Herein, we report the synthesis of functionalized three-dimensional benzophenone analogues derived from [2.2]paracyclophane (pCp). The potential use of these compounds as photocatalysts is disclosed. Benzophenone and its derivatives are well-known photoactive compounds that have been extensively employed over the years as catalysts to promote a variety of transformations activated by light. The development of differently substituted three-dimensional versions of such compounds may significantly expand the range of their applications in photocatalysis. Exploitation of the planar chirality of substituted paracyclophanes may also lead to significant innovations in different fields. [2.2]Paracyclophane-based benzophenone derivatives incorporating reactive ester or amide functions at their pseudo-gem position are successfully prepared in a selective manner. Examples of both racemic and enantiopure compounds are reported. As a proof of concept, the catalytic activities of the newly synthesized molecules are compared to that of benzophenone in a known photooxidation reaction. [ABSTRACT FROM AUTHOR]

Cu/SiO2 catalysts are widely applied to the hydrogenation of dimethyl oxalate and ethylene carbonate to the corresponding ethylene glycol and methanol simultaneously, whereas ethylene glycol and methanol are important bulk commodities and raw materials for the production of oxygen‐containing chemicals and fuels. However, Cu particles usually aggregate or sinter to deactivate and the ratio of surface Cu0/Cu+ species is also difficult to control under the reaction conditions, so that the catalyst activity and stability is still a big challenge. It was found that modification of Cu‐based catalysts with certain organic compound inhibited the agglomeration of Cu particles, regulated the ratio of surface Cu0/Cu+ species, and even generated carbon layers to protect the Cu particles, which definitely improved the stability of the catalyst along with the enhanced catalytic performance. In this review, recent developments in ester hydrogenation over organic compound‐modified Cu/SiO2 catalysts were summarized and the issues to be further clarified are discussed as well. [ABSTRACT FROM AUTHOR]

Herein we describe an efficient methodology for metal‐free hydroborative cleavage of lactones and esters with HBPin (Pin=pinacol) to the corresponding alcohol derivatives using ammonia borane as a pre‐catalyst. The reactions proceed under mild conditions, can be performed in a solvent‐free manner, and do not require an inert atmosphere. Combined experimental and computational mechanistic studies suggest a novel mechanism that involves μ‐aminodiboranes as catalytically active species. [ABSTRACT FROM AUTHOR]

Development of new organic synthetic methods fascinating the researchers which facilitating the increasing demands of the modern society, environmental friendly with high efficiency and low cost. The introduction of chromophores in an organic molecules facilitating intersystem crossing (ISC) to harvest both singlet and triplet excitons is also currently demanding field. We report a facile synthesis of symmetrical azines from carbonyl compounds and hydrazine hydrate with carboxylic acid esters as catalyst in methanol. This reaction presents a condensation of primary amino groups in hydrazine hydrate and carbonyl compounds took place simultaneously in a very short refluxing time. The prepared azines 1–10 were structurally analysed by various analytical techniques such as LC-MS1, H NMR13, C NMR, UV-Vis, FTIR and single crystal X-ray diffraction. Photoluminescence properties of prepared azines were recorded in CCl4 at 1 × 10−3 M and excitation range from 329 to 362 nm. The photoluminescence analysis results revealed that compounds 1–10 (except 8) were showed delayed fluorescence and 8 was showed fluorescence property. The photophysical properties of compounds 1–10 such as electron density and band gap energies was calculated by density function theory. This results revealed that the intra-molecular charge transfer occurs within the azines. The azine function in the azines enabling intersystem crossing hence, it is showing phosphorescence. [ABSTRACT FROM AUTHOR]

Carboxylesterases serve as potent biocatalysts in the enantioselective synthesis of chiral carboxylic acids and esters. However, naturally occurring carboxylesterases exhibit limited enantioselectivity, particularly toward ethyl 3-cyclohexene-1-carboxylate (CHCE, S1), due to its nearly symmetric structure. While machine learning effectively expedites directed evolution, the lack of models for predicting the enantioselectivity for carboxylesterases has hindered progress, primarily due to challenges in obtaining high-quality training datasets. In this study, we devise a high-throughput method by coupling alcohol dehydrogenase to determine the apparent enantioselectivity of the carboxylesterase AcEst1 from Acinetobacter sp. JNU9335, generating a high-quality dataset. Leveraging seven features derived from biochemical considerations, we quantitively describe the steric, hydrophobic, hydrophilic, electrostatic, hydrogen bonding, and π-π interaction effects of residues within AcEst1. A robust gradient boosting regression tree model is trained to facilitate stereodivergent evolution, resulting in the enhanced enantioselectivity of AcEst1 toward S1. Through this approach, we successfully obtain two stereocomplementary variants, DR3 and DS6, demonstrating significantly increased and reversed enantioselectivity. Notably, DR3 and DS6 exhibit utility in the enantioselective hydrolysis of various symmetric esters. Comprehensive kinetic parameter analysis, molecular dynamics simulations, and QM/MM calculations offer insights into the kinetic and thermodynamic features underlying the manipulated enantioselectivity of DR3 and DS6. Carboxylesterases catalyze the enantioselective synthesis of chiral carboxylic acids and esters but exhibit limited enantioselectivity, particularly toward ethyl 3-cyclohexene-1- carboxylate (CHCE). Here, the authors establish a high-throughput method to generate a high-quality dataset for carboxylesterase AcEst1 from Acinetobacter sp. JNU9335 using CHCE as the substrate, use it to train a machine learning predictor and design two stereocomplementary mutants to synthesize both enantiomers of chiral CHCE. [ABSTRACT FROM AUTHOR]

There is a growing demand for herbicides that are more effective than conventional ones yet less harmful to ecosystems. In light of this, this study aimed to synthesize esters from phenols and phenoxyacetic acid, using compounds with known phytotoxic potential as starting materials. Phenoxyacetic acid was first synthesized and then utilized in the synthesis of seven esters through Steglich esterification, employing N,N'-dicyclohexylcarboimide and N,N-dimethylpyridin-4-amine in the presence of phenols (thymol, vanillin, eugenol, carvacrol, guaiacol, p-cresol, and β-naphthol), yielding esters 1–7. All synthesized compounds were characterized using mass spectrometry, 1H, and 13C NMR. These compounds were tested for phytotoxicity to evaluate their effects on the germination and root development of Sorghum bicolor and Lactuca sativa seeds, and for the induction of alterations in the mitotic cycle of meristematic cells of L. sativa roots. Esters 1, 3, 4, and 5 exhibited the most significant phytotoxic activity in both L. sativa and S. bicolor. Alterations in the mitotic index and frequency of chromosomal alterations in L. sativa roots revealed the cytotoxic, genotoxic effects, and the aneugenic mode of action of the tested molecules. These findings suggest that these compounds could serve as inspiration for the synthesis of new semi-synthetic herbicides. [ABSTRACT FROM AUTHOR]

Acyl iodides are expected to be excellent acylating agents due to the low bond dissociation energy of the carbon–iodine bond and the high capability of iodine as a leaving group. Unfortunately, the preparative methods for acyl iodides directly from carboxylic acids are rather limited. In this work, we found that a novel binary system combining I2 and diphenylphosphine oxide (Ph2P(O)H) provides a simple method for the preparation of acyl iodides from carboxylic acids. Furthermore, the subsequent one‐pot reaction with appropriate nucleophiles, such as amines, alcohols, and thiols, afforded the corresponding amides, esters, and thioesters, respectively, in good to excellent yields. [ABSTRACT FROM AUTHOR]

Efficient approaches toward the synthesis of quinazolines and dihydroisoquinolines have been developed through copper‐catalyzed aerobic oxidative dehydrogenation of N‐heterocycles. The dehydrogenation was achieved through copper‐catalyzed aerobic oxidative dehydrogenation and azodicarboxylate esters‐mediated dehydrogenation of amines. Azodicarboxylate esters could be regenerated from copper‐catalyzed dehydrogenation of corresponding hydrazodicarboxylate esters, which made this catalytic dehydrogenation process more efficient and reactive. [ABSTRACT FROM AUTHOR]

Herein the one‐pot thioesterification and hydrothiolation of α, β‐unsaturated esters with aliphatic thiols was reported at room temperature. The mechanism was indirectly revealed which α, β‐unsaturated thioester was the intermediate. The advantages of this method included transition‐metal‐free, mild conditions, broad substrate scope and good functional group tolerance. On the other hand, the hydrothiolation of α, β‐unsaturated aliphatic esters at room temperature was also developed. [ABSTRACT FROM AUTHOR]

Comprehensive Summary A tandem Diels–Alder reaction/Claisen rearrangement/decarboxylation strategy of N‐allenamides (or aryloxyallenes) with 3‐alkoxycarbonyl‐2‐pyrones has been developed for the efficient synthesis of diarylmethanes with moderate to good yields. The reaction exhibits good functional group tolerance and can be applied to late‐stage modifications of known drug molecules. Mechanistic studies indicate that the ester group at the 3‐position of 2‐pyrones is essential, and the initial Diels–Alder reaction between the 2‐pyrones and the proximal C=C bond of the N‐allenamides (or aryloxyallenes) is crucial for the success of the reaction. [ABSTRACT FROM AUTHOR]

A diaminomethylenemalononitrile organocatalyst efficiently promoted the asymmetric conjugate addition of cyclic β‐keto esters to (E)‐β‐nitroacrylate derivatives, yielding the corresponding β‐nitro esters derivatives with excellent enantioselectivities (up to >99 % ee). This is the first successful example of highly stereoselective conjugate addition of cyclic β‐keto esters to (E)‐β‐nitroacrylate derivatives to obtain anti‐isomers. [ABSTRACT FROM AUTHOR]

Selenoxide syn elimination is a widely used method for the synthesis of alkenes because it proceeds under exceptionally mild conditions, typically with excellent regio- and stereoselectivity. Surprisingly, hetero-selenoxide eliminations, where one or both olefinic carbon atoms are replaced with heteroatoms, have been little investigated, and their selenonyl counterparts even less so. A variety of such reactions, where the heteroatoms included combinations of O, N and S, as well as C, were investigated computationally. Selenoxides typically have lower activation energies and are slightly endothermic, while the corresponding selenones display higher activation energies and are exothermic in the gas state. The results are consistent with concerted, five-centre processes, leading to the formation of dioxygen, aldehydes, diazenes and imines from seleninyl or selenonyl peroxides, esters, hydrazines and amines, respectively. The more acidic selenenyl hydrodisulfide analogue undergoes proton transfer to the basic selenoxide oxygen atom instead of concerted elimination, resulting in the formation of a zwitterion. However, the formation of the corresponding selenonyl zwitterion is disfavoured compared to concerted syn elimination. The effects of solvents were also computed along with changes in enthalpy, entropy and free energy. Solvent effects were variable, while free energy calculations indicated overall ΔG values ranging between 3.60 and −32.12 kcal mol−1 for the syn eliminations of methyl methanethioseleninate and methaneperoxyselenonic acid, respectively. These computations suggest that the olefin-forming selenoxide syn elimination may be more general than currently understood and that replacement of the two carbon atoms with heteroatoms can lead to viable processes. [ABSTRACT FROM AUTHOR]

There is need for advancing minimally invasive diagnostic techniques for sex differentiation at early life-stage classes in sea turtles. The objectives of this study were to determine whether there are sex-specific effects on the metabolome of the loggerhead sea turtle (Caretta caretta) and to identify potential biomarkers for sex classification at early life-stage classes (50 post-hatchling and 50 juvenile). Comprehensive analyses including plasma chemistry (n = 100) and untargeted (n = 48) metabolomic analyses were performed. Unlike with plasma chemistry analytes, there were significant differences in the metabolomic profiles between sexes. Nine metabolites differed significantly between sexes, with several metabolites deserving greater attention as potential biomarkers: C22H32O6 and pantothenic acid was higher in females than in males, and carboxylic acid ester (C10H16O5), 1-methylhistidine and C7H14N2O7 was higher in males than females. These differences remained constant both across and within the same life-stage class. This work identified a discernible effect on the metabolic profile based on sex of loggerhead sea turtles and it suggests that these metabolites and/or their ratios could serve as potential biomarker candidates for sex classification in this species. This study demonstrates a distinct metabolomic profile between male and female loggerhead turtles at different physiological stages (posthatchling and juvenile animals) and proposes biomarkers for sex classification. [ABSTRACT FROM AUTHOR]

An efficient one-step procedure for the synthesis of a new series of multifunctional olefins by condensation of α-substituted β-diketones as well as β-phosphonoesters and benzoylated β-ketoesters with formaldehyde, using potassium carbonate in refluxing THF, followed by a deacylation reaction, is herein described. In contrast, the α-substituted β-keto esters, bearing an acyl moiety, only undergo a hydroxymethylation reaction, with no metal catalysts/activating agents, as is usually required for the process, affording the corresponding α-hydroxymethyl β-keto esters in high yields. [ABSTRACT FROM AUTHOR]

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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.)

A simple and efficient strategy has been developed for the synthesis of organic nitrate esters via visible‐light‐induced multi‐component nitrooxylation reactions of α‐diazoesters, cyclic ethers, and tert‐butyl nitrite under open air atmosphere. This transformation could be conducted under mild and metal‐free conditions to provide a number of organic nitrate esters in moderate to good yields using air as the green oxidant. [ABSTRACT FROM AUTHOR]

A ZnO‐mediated benzoylation between carvone oxime and acyl is reported, enabling access to diverse carvone oxime ester and carvone oxime sulfonic esters under solvent‐free conditions. The operationally simple procedure provides a novel method for the synthesis of oxime‐ester bonds with excellent chemo selectivity. This strategy provides a mild, direct, and green approach for synthesizing carvone oxime ester in moderate to excellent yields with good substrate tolerance. In addition, carvone oxime was synthesized under solvent‐free conditions. [ABSTRACT FROM AUTHOR]

We disclose herein a triflic acid and silane‐promoted reductive deoxygenative transformation of ketoacid/esters for the divergent synthesis of different‐sized lactones, which hold substantial significance in pharmaceutical and natural product chemistry. Owing to the simple reaction conditions and setup, this protocol features broad substrate generality, scalability, and good functional group tolerance, including late‐stage functionalization of pharmaceutical compounds and natural products. The control experiments and detailed NMR study provide insight into the reaction mechanism. [ABSTRACT FROM AUTHOR]

A mild, metal‐free Giese‐type hydrodifluoroalkylation of electron‐deficient alkenes under visible‐light irradiation has been developed. This highly reducing photoactivated Hantzsch ester facilitates C(sp3)−CF2 bond formation through photoinduced electron transfer (PET) and hydrogen atom transfer (HAT) processes, providing an easy access to diverse gem‐difluorinated alkanes. [ABSTRACT FROM AUTHOR]

Readily accessible (PSi)Ni(II)‐benzyl complexes supported by bidentate phosphino(silyl) ligation were found to be effective pre‐catalysts for the direct hydrogenation of a variety of highly sterically hindered, unfunctionalized alkenes under relatively mild conditions (2.5‐5 mol% Ni, 10 atm H2, 50 °C) and without the need for additional additives or activator species. A range of substrates, including di‐, tri‐, and tetra‐substituted alkenes were evaluated in this regard and afforded good to moderate yields. Substrates featuring α,β‐unsaturated carbonyl functionality were also readily hydrogenated with no evidence for reduction of carbonyl or ester C−O functionalities. Deuteration experiments highlight the occurrence of chain walking which occurs in the background of the reported catalytic chemistry. [ABSTRACT FROM AUTHOR]

Current routes to boronic acids and their corresponding esters to be used in subsequent Suzuki–Miyaura (SM) cross couplings impact the cost, waste, and safety concerns associated with generating these materials. A new method for installing the ethyl pinacol boronic ester, or B(Epin) derivative leads to stable borylated products under near-neat conditions using high concentrations of a green solvent and moderate reaction temperatures, catalyzed by relatively low palladium loadings. Alternatively, the newly fashioned Ar–B(Epin) can be generated in situ and used directly in the same pot for SM reactions leading to aromatic and heteroaromatic residues characteristic of the biaryl products being formed. An array of complex targets, including API-related products, can be generated via this green and environmentally responsible methodology. [ABSTRACT FROM AUTHOR]

We report the first switchable acylation of H-phosphonate with chloroformate. The acylation site (P vs. O) in H-phosphonate was switched by changing the acyl pyridinium/ammonium ions. Unexpected phosphite formation was observed during the O-acylation of H-phosphonate. Twenty-six structurally diverse phosphotriesters and phosphonoformate esters were synthesized in microflow reactors. [ABSTRACT FROM AUTHOR]

Lawesson’s reagent reacted with racemic diethyl malate to yield O-(1,2-bis(ethylcarboxylate)ethyl-1 4-methoxyphenyl dithiophosphonic acid. The acid formed pyridinium dithiophosphonate salts with 3-(hydroxymethyl)pyridine, pyridoxine, and (S)-(–)-nicotine. The salts revealed antifungal activity against Candida albicans. [ABSTRACT FROM AUTHOR]

A metal-free strategy has been developed for the α-arylation of carboxylic acids, secondary amides, and esters employing arenes as key reagents. This process entails the Lewis-acid catalyzed reductive Friedel–Crafts alkylation of arenes utilizing α-ketoacids, facilitated by silane in HFIP solvent. The transformation exhibits exceptional functional group tolerance, enabling late-stage functionalization of natural products. This one-step protocol has been successfully used to synthesize commercially available drugs, such as adiphenine, piperidolate, derivatives of ketoprofen, ibuprofen, flurbiprofen, and the pesticide bromopropylate. [ABSTRACT FROM AUTHOR]

This study involves the synthesis of asterism compounds (D1-D6) through the reaction of 1 mole of benzene 1,3,5-triol with 3 moles of prepared pentacyclic ring ester derivatives, dissolved in absolute ethanol. The validity of the compound structures was confirmed using physical and spectroscopic methods such as infrared spectroscopy, and proton nuclear magnetic resonance spectroscopy. Additionally, melting points and purity were determined, and reaction progress was monitored by Thin-Layer Chromatography (TLC). The liquid crystal phases of certain prepared compounds were examined using a polarizing optical microscope (POM). [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]

Epothilones are 16‐membered macrolides that act as microtubule‐targeting agents to tackle cancer. Many synthetic analogues have been investigated for their activity, yet often based on macrolide structures. A notable exception is Ixabepilone, an azalide whose metabolic stability and pharmacokinetics are significantly improved. Exploiting the amide‐triazole bioisosterism, in this work we report the synthesis of the first generation of epothilones lacking the macrolide or azalide structure, with the ester or amide linkage replaced by a triazole unit. Together with the synthesis of this new analogue, computational and biological evaluations have been performed too. [ABSTRACT FROM AUTHOR]

This study examines and compares the breakdown and aging properties of five insulating liquids. Additionally, the influence of different voltage polarities on these properties was analyzed to investigate the effect of aging on polarity behavior under lightning impulse voltage in a semi-uniform field. The results were compared to standardized AC breakdown tests. After 2330 h and 4350 h of aging, changes were observed in key aging indicators such as water content (both absolute and relative), total acid number, and color across all liquids. Viscosity increased by up to 10% in natural esters. Notably, the rise in water content due to aging was concerning only for mineral oil, exceeding 20%. The impact of aging on breakdown voltage varied depending on the voltage type and polarity. Aging had the least effect under negative lightning impulse voltage, while the synthetic ester MIDEL 7131 exhibited the most significant reduction in breakdown voltage under positive lightning impulse voltage, dropping by over 24%, from more than 560 kV to 428 kV. In contrast, mineral oil showed only a 3% decrease. For the other liquids, the most pronounced reduction in breakdown voltage due to aging occurred under AC voltage, with natural esters showing a 17% decline, synthetic esters 26%, and mineral oil experiencing a 38% reduction. [ABSTRACT FROM AUTHOR]

In this study, a difluorocarbene‐promoted O−O bond activation of peroxy acids is developed through the insertion of difluorocarbene into O−H bond. This activation strategy in synergy with O−B coordination with boronic acids/ester greatly polarizes the O−O bond for in‐situ generation of carboxylium species that reacts with the nucleophilic part of boronic acids in a concerted way to produce carboxylic esters. Good efficiency and functional group tolerance are demonstrated. Application of this method to the functionalization of a boronic acid drug used as HSL enzyme inhibitor produces smoothly the ester derivative. This difluorocarbene‐mediated O−O bond activation strategy is conceptually different from traditional radical type methods, and is also complementary to conventional esterification methods with a distinct retro‐synthetic disconnection. [ABSTRACT FROM AUTHOR]

The selective functionalization of 1,3-bis(boronic) esters holds the potential for creating diverse molecular structures, particularly through the late-stage functionalization of the remaining C–B bond. By employing distinct organometallic reagents, we have developed a method for regiodivergent alkynylation of 1,3-bis(boronic) esters, facilitated by unique chelation patterns. Notably, this methodology effectively overcomes limitations commonly encountered in radical chemistry, which generates only monoselective downstream targets. Furthermore, the compounds synthesized through this approach can serve as significant building blocks, contributing to the construction of molecular complexity. [ABSTRACT FROM AUTHOR]

Metal triflate-catalyzed acylation of sulfonamides and direct transacylation of N-acylsulfonamides have been investigated. The acylation of sulfonamides proceeds efficiently in the presence of a catalytic amount of Cu(OTf)2 (0.001 equiv) using either carboxylic anhydrides or acyl chlorides as the acylating agents. Alternative catalysts suitable for this transformation include Al(OTf)3, Fe(OTf)3, Ga(OTf)3, In(OTf)3, and Er(OTf)3. In the presence of Cu(OTf)2 (0.2 equiv), N-acylsulfonamides undergo direct transacylation in excess acyl chlorides (10 equiv) to furnish new N-acylsulfonamides through exchange of N-acyl groups. Ga(OTf)3, Fe(OTf)3, and In(OTf)3 are similarly reactive in catalyzing such transacylation transformations. The reaction conditions are mild and operationally convenient. A variety of functional groups including halogeno, keto, nitro, cyano, ether, and carboxylic ester are tolerated, providing the corresponding monoacylated N-acylsulfonamides in good to excellent yields. [ABSTRACT FROM AUTHOR]