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We present a computational study of the structure and of the transport properties of electrolytes based on Li[(CF₃SO₂)₂N] solutions in mixtures of sulfoxides and sulfones solvents. The simulations of the liquid phases have been carried out using molecular dynamics with a suitably parametrized model of the intermolecular potential based on a polarizable expression of the electrostatic interactions. Pulse field gradient NMR measurements have been used to validate and support the computational findings. Our study show that the electrolytes are characterized by extensive aggregation phenomena of the support salt that, in turn, determine their performance as conductive mediums. [ABSTRACT FROM AUTHOR]

A visible‐light‐induced photoredox‐catalyzed radical tandem cyclization of o‐isocyanodiaryl amines with arylthiodifluoroalkyl 2‐pyridyl sulfones or difluormethyl bromides has been realized for the first time. The reaction works with a broad range of substrates and provides a simple and efficient method for the synthesis of 11‐difluoromethyl‐substituted dibenzodiazepines from easily available starting materials in very mild conditions. [ABSTRACT FROM AUTHOR]

A one-step method to convert nitroarenes into aryl sulfones under operationally simple, transition-metal-free conditions is described. A range of nitroarenes were reacted with sodium sulfinates and caesium carbonate in N , N ′-dimethylpropyleneurea to afford aryl sulfones in up to 83% yield. [ABSTRACT FROM AUTHOR]

In recent years, Sulfonyl hydrazides have emerged as powerful reagents for sulfonyl sources because of their easy availability, stability, and non-toxic nature. The hydrazinyl group can be easily detached from sulfonyl hydrazides using oxidative, thermal, radical, basic, or metal-catalyzed conditions. In this review, we have collected recent protocols for preparing sulfones, sulfides, and sulfoxides from the ideal starting material, sulfonyl hydrazides using various transition metals or in metal-free conditions. [ABSTRACT FROM AUTHOR]

Directly with arylsulfonyl chlorides, a green and efficient deborylativesulfonylation of aryl(alkenyl)boronic acids has been developed to access both diarylsulfones and vinylarylsulfones in moderate to excellent yields at room temperature under visible‐light irradiation. This protocol features broad C(sp2)‐arylsulfone applicability, simple operation, accessibility of raw materials and ease of scale‐up. The key to the success of this photoredox transformation is introducing catalytic amounts of additives, naphthalen‐2‐ols, thus boosting the formed electron donor‐acceptor (EDA) complexes, which can dramatically improve not only the reaction efficiency but also the selectivity. This strategy was inspired and derived from specific substrates, representing a rare paradigm of how to exploit a more general reaction system. Moreover, extensive control experiments provide insights into the proposed mechanism. [ABSTRACT FROM AUTHOR]

In synthetic carbohydrate chemistry, the modification of glycosyl radicals pathway stands as a central area of focus. The radical‐based reactions often demonstrate remarkable compatibility with various functional groups owing to the mild initiation conditions. In particular, the identification of novel glycosyl radical precursors, combined with advanced reaction techniques, has substantially broadened the scope of glycosyl compound synthesis. Despite the presence of versatile donors, the synthesis of noble donors is still addressed as a synthetic need and challenges associated with sugar chemistry. Currently, a new class of glycosyl radical precursors has been developed which enables the production of C‐, S‐, O‐, and N‐glycosides efficiently. In this light, we highlight strategies towards bench‐stable glycosyl sulfoxides, sulphone, and sulfite donors that can enable the site‐, regio‐ and stereoselective transformation of protected or naked sugar synthons in synthetic carbohydrate chemistry. Here, this review article covers the recent developments in the selective glycosyl radical diversification such as glycosyl alkylation, arylation, alkenylation, sulfuration, C−H activation, and DNA conjugation via the bench‐stable donors along with mechanistic aspects, challenges, and future directions. [ABSTRACT FROM AUTHOR]

Benzoheteroles are promising structural scaffolds in the realm of medicinal chemistry, but sustainable synthesis of 2,3‐difunctionalized benzoheterole derivatives is still in high demand. Indeed, we have conceptually rationalized the intrinsic reactivity of propargylic‐enyne systems for the flexible construction of 2,3‐disubstituted benzoheteroles through radical sulfonylative‐cyclization cascade under organophotoredox catalysis. We hereby report an efficient visible‐light‐induced sulfonyl radical‐triggered cyclization of 1,6‐enynols with sulfinic acids under the dual catalytic influence of 4CzIPN and NiBr2⋅DME, which led to the formation of 2,3‐disubstituted benzoheteroles in good to high yields. Additionally, the Rose Bengal (RB)‐catalyzed radical sulfonylative‐cycloannulation of acetyl‐derived 1,6‐enynols with sulfinic acids under blue LED irradiation allowed to access 3‐(E‐styryl)‐derived benzofurans and benzothiophenes in moderate to good yields. The scope and limitations of the present strategies were successfully established using different classes of 1,6‐enynols and sulfinic acids bearing various sensitive functional groups, yielding the desired products in a highly stereoselective fashion. Plausible mechanistic pathways were also proposed based on the current experimental and control experiments. [ABSTRACT FROM AUTHOR]

Comprehensive Summary Enhancing the DNA toolbox with innovative photochemical reactions is pivotal for advancing nucleic acid‐based technologies. Aldehyde groups, versatile bioorthogonal handles for imine formation under acidic conditions, are particularly valuable due to their roles in nucleic acid epigenetics. Here, we present the first photocatalytic on‐DNA aldehyde allylation, enabling precise DNA functionalization under mild, neutral aqueous conditions. Our approach utilizes a photocatalytic polarity‐reversal reaction between DNA‐conjugated benzaldehydes and allyl sulfones. This reaction demonstrates exceptional chemoselectivity while preserving DNA integrity. By varying allyl sulfones, we achieve site‐specific labeling of non‐native DNA with the aldehyde group and cross‐linking with DNA‐bearing allyl sulfones. Furthermore, our method facilitates selective labeling and pull‐down enrichment of 5‐formylpyrimidine nucleotides among complex cellular DNA. This photocatalytic on‐DNA aldehyde transformation expands the limited bioorthogonal photochemical toolboxes, providing novel avenues for functionalizing both non‐native and native aldehyde modifications on DNA. [ABSTRACT FROM AUTHOR]

An efficient route for the chemoselective deoxygenation of benzylphenyl sulfones to the corresponding sulfides has been developed using a mixture of 1,2-bis(diphenylphosphino)ethane(dppe) and NBS as an effective promoter. This is the first development on the deoxygenation of diverse benzylphenyl sulfones under metal-free conditions. The mild reaction conditions, formation of the water soluble by-product and tolerance of a wide range of functional groups promote its broad applications in organic synthesis. [ABSTRACT FROM AUTHOR]

Allylic sulfones are valuable motifs due to their medicinal and biological significance and their versatile chemical reactivities. While direct allylic C−H sulfonylation represents a straightforward and desirable approach, these methods are primarily restricted to terminal alkenes, leaving the engagement of the internal counterparts a formidable challenge. Herein we report a photocatalytic approach that accommodates both cyclic and acyclic internal alkenes with diverse substitution patterns and electronic properties. Importantly, the obtained allylic sulfones can be readily diversified into a wide range of products, thus enabling formal alkene transposition and all‐carbon quaternary center formation through the sequential C−H functionalization. [ABSTRACT FROM AUTHOR]

Here, we report a robust nickel‐catalyzed α,β‐dehydrogenation process designed for substrates that contain electron‐withdrawing sulfur and phosphorus groups. Leveraging the formation of organozinc intermediates and the utilization of a mild oxidant, allyl methyl carbonate, this methodology exhibits remarkable efficiency and outstanding diastereoselectivities across a diverse array of substrates, achieving E : Z ratios exceeding 20 : 1. Investigation through deuterium incorporation studies and an analysis of the reaction sequence leading to the formation of the dehydrogenative allylation side product, provide useful insights into reaction optimization. [ABSTRACT FROM AUTHOR]

BACKGROUND: A broad suite of bisphenol S (BPS) derivatives as alternatives for BPS have been identified in various human biological samples, including 4-hydroxyphenyl 4-isopropoxyphenylsulfone (BPSIP) detected in human umbilical cord plasma and breast milk. However, very little is known about the health outcomes of prenatal BPS derivative exposure to offspring. OBJECTIVES: Our study aimed to investigate the response of hepatic cholesterol metabolism by sex in offspring of dams exposed to BPSIP. METHODS: Pregnant ICR mice were exposed to 5μg/kg body weight (BW)/day of BPSIP, BPS, or E2 through drinking water from gestational day one until the pups were weaned. The concentration of BPSIP, BPS, or E2 in the plasma and liver of pups was determined by liquid chromatography-tandem mass spectrometry. Metabolic phenotypes were recorded, and histopathology was examined for liver impairment. Transcriptome analysis was employed to characterize the distribution and expression patterns of differentially expressed genes across sexes. The metabolic regulation was validated by quantitative real-time PCR, immunohistochemistry, and immunoblotting. The role of estrogen receptors (ERs) in mediating sex-dependent effects was investigated using animal models and liver organoids. RESULTS: Pups of dams exposed to BPSIP showed a higher serum cholesterol level, and liver cholesterol levels were higher in females and lower in males than in the controls. BPSIP concentration in the male liver was 1.22±0.25 ng/g and 0.69±0.27 ng/g in the female liver. Histopathology analysis showed steatosis and lipid deposition in both male and female offspring. Transcriptome and gene expression analyses identified sex-specific differences in cholesterol biosynthesis, absorption, disposal, and efflux between pups of dams exposed to BPSIP and those in controls. In vivo, chromatin immunoprecipitation analysis revealed that the binding of ERα protein to key genes such as Hmgcr, Pcsk9, and Abcg5 was attenuated in BPSIP-exposed females compared to controls, while it was enhanced in males. In vitro, the liver organoid experiments demonstrated that restoration of differential expression induced by BPSIP in key genes, such as Hmgcr, Ldlr, and Cyp7a1, to levels comparable to the controls was only achieved when treated with a combination of ERα agonist and ERβ; agonist. DISCUSSION: Findings from this study suggest that perinatal exposure to BPSIP disrupted cholesterol metabolism in a sex-specific manner in a mouse model, in which ERa played a crucial role both in vivo and in vitro. Therefore, it is crucial to systematically evaluate BPS derivatives to protect maternal health during pregnancy and prevent the transmission of metabolic disorders across generations [ABSTRACT FROM AUTHOR]

The transition metal‐catalyzed multi‐component cross‐electrophile sulfonylation, which incorporates SO2 as a linker within organic frameworks, has proven to be a powerful, efficient, and cost‐effective means of synthesizing challenging alkyl–alkyl sulfones. Transition metal catalysts play a crucial role in this method by transferring electrons from reductants to electrophilic organohalides, thereby causing undesirable side reactions such as homocoupling, protodehalogenation, β‐hydride elimination, etc. It is worth noting that tertiary alkyl halides have rarely been demonstrated to be compatible with current methods owing to various undesired side reactions. In this work, a zinc‐promoted cross‐electrophile sulfonylation is developed through a radical‐polar crossover pathway. This approach enables the synthesis of various alkyl–alkyl sulfones, including 1°‐1°, 2°‐1°, 3°‐1°, 2°‐2°, and 3°‐2° types, from inexpensive and readily available alkyl halides. Various functional groups are well tolerated in the work, resulting in yields of up to 93%. Additionally, this protocol has been successfully applied to intramolecular sulfonylation and homo‐sulfonylation reactions. The insights gained from this work shall be useful for the further development of cross‐electrophile sulfonylation to access alkyl–alkyl sulfones. [ABSTRACT FROM AUTHOR]

We report here a mild process to access diversely functionalized enantioenriched β‐gem‐difluorinated (S)‐alcohols by using biocatalytic reduction in >99% yield and enantiomeric excesses ranging from 96% to >99%. This novel approach involves enzymatic reduction of α‐gem‐difluorinated heterocyclic and carbocyclic ketone derivatives as well as an acyclic gem‐difluorinated β‐ketosulfone and proceeds under mild conditions at 30 °C under aqueous conditions to produce a range of high added value enantioenriched difluorinated alcohols including 3,3‐difluorochromanol, 3,3‐difluorothiochromanol, 3,3‐difluoro‐dihydroquinolinol, and α‐difluorinated β‐hydroxysulfone derivatives. A comparative study between enzymatic reduction and metal‐catalyzed asymmetric transfer hydrogenation was carried out as well. [ABSTRACT FROM AUTHOR]

Comprehensive Summary: An alkyl radical initiated cyclization/tandem reaction of alkyl bromides and alkyl electrophiles by using potassium metabisulphite (K2S2O5) as a connector is developed for the synthesis of various lactam‐substituted alkyl sulfones. Notably, this process does not require a metal catalyst or metal powder reductant, highlighting its environmentally friendly features. The reaction demonstrates outstanding substrate adaptability and a high tolerance towards diverse functional groups. Furthermore, the biologically active molecules and commercially available drugs with a late‐stage modification are also highly compatible with this transformation. Mechanistic studies revealed that the reaction proceeds through a single‐step process involving intramolecular radical cyclization, "SO2" insertion, and external alkyl incorporation. [ABSTRACT FROM AUTHOR]

Sulfonyl chlorides are a synthetically attractive source of sulfonyl radicals in photoredox catalysis and are useful precursors in the synthesis of sulfones. Sulfamoyl chlorides, on the other hand, remain poorly represented despite their similar potential. In this study, N‐chlorosulfonylated β‐lactams were prepared from readily available precursors and utilized in an atom transfer radical addition (ATRA) reaction with a variety of olefins, producing β‐lactam sulfonamides in 49–95% yields. β‐Lactams fused to a dihydro‐1,2‐thiazine ring which closely resemble carbacephems, a widely used class of antibiotics, were also synthesized by an intra‐molecular ATRA reaction. This methodology enables the preparation of β‐lactam sulfonamides, a class of compounds that are of great interest in pharmacology. [ABSTRACT FROM AUTHOR]

Cyclopropanes are among the most important structural units in natural products, pharmaceuticals, and agrochemicals. Herein, we report a manganese-catalyzed cyclopropanation of allylic alcohols with sulfones as carbene alternative precursors via a borrowing hydrogen strategy under mild conditions. Various allylic alcohols and arylmethyl trifluoromethyl sulfones work efficiently in this borrowing hydrogen transformation and thereby deliver the corresponding cyclopropylmethanol products in 58% to 99% yields. Importantly, a major benefit of this transformation is that the versatile free alcohol moiety is retained in the resultant products, which can undergo a wide range of downstream transformations to provide access to a series of functional molecules. Mechanistic studies support a sequential reaction mechanism that involves catalytic dehydrogenation, Michael addition, cyclization, and catalytic hydrogenation. Developing readily available and bench-stable reagents for the cyclopropanation of olefins is needed as traditional methodologies mainly rely on carbene-based strategies. Herein, the authors report a manganese-catalyzed cyclopropanation of allylic alcohols with sulfones via a borrowing hydrogen strategy under mild conditions. [ABSTRACT FROM AUTHOR]

Continuously exacerbating situation of global warming can be effectively mitigated by controlling carbon emissions from combustion processes through economically attractive membrane technology. Carbon capture efficiency of prospective membranes can be significantly improved via synergistically incorporating CO2‐selective ZIF‐300 nanoparticles and carbon nanotubes (CNTs) into polysulfone (PSF) matrix. Solution‐casting coupled with phase‐inversion processes were employed to concoct hybrid membranes containing varying loadings of both nanofillers. Manufactured composite membranes showed improved matrix structure, uniform nanofillers scattering, enhanced thermal resistance, and ameliorated nanofillers‐polysulfone interfacial adhesion as evidenced by morphological and thermal analysis. Both sorption and permeation measurements for CO2 and N2 gases performed on created membranes indicated upgraded CO2 permeability and CO2/N2 permselectivity on account of collegial impact of added nanofillers. In contrast to pristine polysulfone membrane rendering CO2 intake of 4.1 and CO2/N2 sorption selectivity of 12, hybrid membrane containing 15% ZIF‐300 and 3% CNTs uplifted corresponding values to 12 and 22, respectively. As compared to unadulterated polysulfone membrane, CO2 permeability and CO2/N2 permselectivity of hybrid membrane doped with optimized nanofillers loading of were, respectively, elevated by five‐ and three‐folds. Unique features of manufactured membranes can best be manifested in terms of their ability to maintain gas separation performance from post‐combustion effluents. [ABSTRACT FROM AUTHOR]

The development of new catalytic methods based on lower-cost metals under environmentally friendly conditions is still a challenge. Herein, we report an efficient strategy for the synthesis of vinyl sulfones from O -propargyl alkynes and sodium salts of sulfinic acids using silver nitrate, an inexpensive and readily available catalyst, under air atmosphere using aqueous conditions. The products were obtained in good to moderate yields, and the mechanism of the reaction was also investigated. [ABSTRACT FROM AUTHOR]

Vinyl sulfones are crucial building blocks in synthetic chemistry and core structural units of pharmaceutically active molecules, thus extensive investigations have been conducted on the construction of these skeletons. In contrast to the classical synthetic approaches, the radical sulfonylation of alkynes for producing vinyl sulfones has garnered considerable interest because of its mild conditions and high efficiency. Radical sulfonation of alkynes typically begins with the sulfonyl radical attacking the alkynes, followed by further functionalization. Moreover, the association of metal‐catalyst‐free systems with multicomponent reactions (MCRs) offers an environmentally friendly pathway for efficiently constructing complex scaffolds from readily available partners. However, there is no comprehensive review summarizing the advancements in metal‐catalyst‐free multicomponent radical sulfonylation of alkynes. Hence, we provide a categorical overview based on the objects of sulfonylation of alkynes (hydrosulfonylation, carbosulfonylation, aminosulfonylation, oxysulfonylation, sulfosulfonylation, selenosulfonylation, and iodosulfonylation), along with interpretations of the reaction mechanisms. [ABSTRACT FROM AUTHOR]

This study explores the impact of sulfur oxidation on the structural, optical, and electronic properties of [1]benzothieno[3,2-b][1]benzothiophene (BTBT) derivatives, specifically focusing on 2,7-dibromo BTBT (2,7-diBr-BTBT) and its oxidized forms, 5,5-dioxide (2,7-diBr-BTBTDO) and 5,5,10,10–tetraoxide (2,7-diBr-BTBTTO). The bromination of BTBT followed by sequential oxidation with m-chloroperoxybenzoic acid yielded the target compounds in good yields. They were characterized using a wide array of analytical techniques including different spectroscopic methods, X-ray analysis, thermal analysis, and quantum chemical calculations. The results revealed that sulfur oxidation significantly alters the crystal packing, thermal stability, and optoelectronic properties of BTBT derivatives. Notably, the oxidized forms exhibited increased thermal stability and enhanced emission properties, with quantum yields exceeding 99%. These findings provide valuable insights for designing advanced organic semiconductors and fluorescent materials with tunable properties, based on the BTBT core. [ABSTRACT FROM AUTHOR]

This study aimed to develop PSU membranes by adding different concentrations (zero, 0.5, 1.0, and 1.5 wt.%) of graphene nanoplatelets (GNP) during synthesis to evaluate the influence of GNP on membrane permeability, retention capacity, mechanical and chemical resistance, structure, and membrane chemistry. All produced membranes had a hydrophilic character, which reduced with the increase in GNP content (72.4° to 84.4°) and a decrease in thickness (200.8 µm to 109.3 µm). Adding GNP did not affect the membranes' mechanical properties and chemical resistance. GNP addition increased the compaction time (from 5.35 h to 35.62 h) and reduced membrane permeability (from 6.78 L∙m−2∙h−1∙bar−1 to 0.10 L∙m−2∙h−1∙bar−1) of pure water. The obtained membranes were classified as ultrafiltration membranes, with an egg albumin retention rate (45 kDa) above 80 %. A greater retention of egg albumin was observed with the highest amount of GNP (1.5 wt.%). Adding GNP stabilized the polymeric matrix (PSU) properties, including increased chemical and mechanical resistance, interaction between the polymer and the nanofiller, and hydrophobic characteristics with a smaller thickness. This study contributed to Brazilian research in membrane synthesis, promoting the investigation of outstanding materials in the field of nanotechnology, in particular, the use of GNP as an additive in the preparation of mixed matrix membranes for water treatment. [ABSTRACT FROM AUTHOR]

Herein, we report an efficient and sustainable manganese‐catalyzed α‐C−H bond alkylation methodology to synthesize branched sulfones via a hydrogen borrowing pathway. The air‐stable and phosphine‐free Mn‐catalyst, (NNN)Mn(II)Cl2 was synthesized by using an earth‐abundant, commercially available, and inexpensive precursor MnCl2.4H2O, and a stable NNN pincer i. e. [N‐((benzimidazole‐2‐yl)methyl)quinoline‐8‐amine] ligand system. Taking benzyl phenyl sulfones as substrates, and benzyl alcohol derivatives as alkylating agents, a range of branched sulfones were synthesized in 40–82 % isolated yields using (NNN)Mn(II)Cl2 complex as the catalyst under open‐air conditions. Control experiments and deuterium incorporation studies have also been conducted to investigate the possible reaction mechanism and to provide evidence for the hydrogen borrowing pathway. [ABSTRACT FROM AUTHOR]

Chiral γ-keto sulfones are significant structures in both organic synthesis and pharmaceutical chemistry. Although there are many choices for obtaining racemic forms, only a few enantioselective methods have been reported. We have developed a simple way for obtaining chiral γ-keto sulfones in moderate yields and moderate enantiomeric ratios. Readily available sulfinates were directly used as substrates that could be converted into sulfinic acids by treatment with boric acid. The bifunctional catalyst forms a chiral ion pair with the sulfinic acid and controls the enantioselectivity of the sulfonation through hydrogen bonding. [ABSTRACT FROM AUTHOR]

A first metal‐free protocol for the synthesis of allylic sulfones featuring aldehyde functionality at the δ‐position has been reported. The formation of structurally complex δ,δ‐dimethoxy allylic sulfones is enabled by the direct nucleophilic attack of methoxide onto the sulfone‐containing 1,3‐enynes. The present approach allows facile installation of acetal groups within the allylic sulfone scaffold, providing versatile platforms for further functionalization and drug development. [ABSTRACT FROM AUTHOR]

Atropisomers hold significant fascination, not only for their prevalence in natural compounds but also for their biological importance and wide‐ranging applications as chiral materials, ligands, and organocatalysts. While biaryl and heterobiaryl atropisomers are commonly studied, the enantioselective synthesis of less abundant heteroatom‐linked non‐biaryl atropisomers presents a formidable challenge in modern organic synthesis. Unlike classical atropisomers, these molecules allow rotation around two bonds, resulting in low barriers to enantiomerization through concerted bond rotations. In recent years the discovery of new configurationally stable rare non‐biaryl scaffolds such as aryl amines, aryl ethers and aryl sulfones as well as innovative methodologies to control their configuration have been disclosed in the literature and constitute the topic of this minireview. [ABSTRACT FROM AUTHOR]

Cyclic sulfones have demonstrated important applications in drug discovery. However, the catalytic and enantioselective synthesis of chiral cyclic sulfones remains challenging. Herein, we develop nickel‐catalyzed regiodivergent and enantioselective hydroalkylation of sulfolenes to streamline the synthesis of chiral alkyl cyclic sulfones. The method has broad scope and high functional group tolerance. The regioselectivity can be controlled by ligands only. A neutral PYROX ligand favors C3‐alkylation whereas an anionic BOX ligand favors C2‐alkylation. This control is kinetic in origin as the C2‐bound Ni intermediates are always thermodynamically more stable. Reactivity study of a wide range of relevant Ni intermediates reveal a NiI/NiIII catalytic cycle with a NiII−H species as the resting state. The regio‐ and enantio‐determining step is the insertion of this NiII−H species into 2‐sulfolene. This work provides an efficient catalytic method for the synthesis of an important class of organic compounds and enhances the mechanistic understanding of Ni‐catalyzed stereoselective hydroalkylation. [ABSTRACT FROM AUTHOR]

Complexes [(bpy)2Ru(BL)](PF6)2 (Ru(BL), BL=N,N‐di(pyridin‐2‐yl)‐1,10‐phenanthrolinamine) have been investigated in the coupling reaction of aryl halides and sodium arylsulfinates under visible light irradiation. The position (3, 4 or 5) of the nickel‐coordinating di(pyridin‐2‐yl)amine fragment in the 1,10‐phenanthroline core has a strong influence on the activity of the catalytic system. The advantage of binding fragments of photocatalyst and metal complex into one molecule in the systems with bridging ligands N,N‐di(pyridin‐2‐yl)‐1,10‐phenanthrolin‐3‐amine (BL1) and N,N‐di(pyridin‐2‐yl)‐1,10‐phenanthrolin‐4‐amine (BL2), in comparison with mixed catalytic systems, is shown. With Ru(BL2) photocatalysts it is possible to reduce the loading to 0.1 mol%, instead of the commonly used 1–2 mol%, and to eliminate the use of the additional ligand for nickel. Under these conditions, more than 20 diarylsulfones of different structures were synthesized in 25–95% yields. [ABSTRACT FROM AUTHOR]

We here describe a visible-light photooxidation of sulfinate salts with common alkenes to yield β-hydroxy sulfones on DNA. This process demonstrates a broad substrate compatibility and achieves conversion rates ranging from moderate to excellent. Most importantly, it presents a straightforward, efficient, and metal-free approach for synthesizing Csp3-rich DNA-encoded libraries. [ABSTRACT FROM AUTHOR]

Polyphenylene sulfide sulfone (PPSS) was synthesized by one-step method and utilized as a sizing agent for carbon fibers. The effects of various monomer ratios, reaction time, and reaction temperature were investigated on the molecular weight of PPSS. The thermal analysis revealed that the product PPSS exhibited a glass transition temperature exceeding 215.5°C, indicating exceptional thermal stability. After PPSS sizing treatment, the grooves on the surface of carbon fibers were filled, resulting in a substantial enhancement of the micro interface properties. The surface energy was increased by 8.2%, while the maximum weight loss temperature was 27.8% higher than that of the commercial carbon fiber. The tensile strength of the carbon fiber after heat treatment reached 2196 MPa, representing a 45.9% increase over that of the commercial carbon fiber. [ABSTRACT FROM AUTHOR]

A method for the synthesis of γ‐amino sulfones through visible light‐induced oxidative decarboxylation and radical reductive addition is described. Various readily available N‐protected natural amino acids react with aromatic/aliphatic vinyl sulfones to directly produce γ‐amino sulfone derivatives. This reaction is also applicable to α‐N(O)‐acids and other aliphatic carboxylic acids, resulting in the corresponding sulfone derivatives. The method operates without the need for sacrificial reducing agents or additional hydrogen atom donors. The sole by‐product is CO2 released from decarboxylation, rendering the process both atom‐ and step‐economical. [ABSTRACT FROM AUTHOR]

In this paper, composite proton exchange membranes (PEMs) based on functionalized graphene oxide (NGO) and carboxylated sulfonated poly aryl ether ketone sulfone (C-SPAEKS) were successfully synthesized. Functionalized graphene oxide was synthesized using graphene oxide as a substrate, and then diethylenetriamine (DETA) was chemically bound to the graphene oxide. The 1H NMR, FT-IR and XPS were used to characterize the NGO and composite membranes. The results show that the composite membranes have good proton conductivity, dimensional stability and electrochemical performance. The swelling rate of all the composite membranes was less than 18%, which indicates that they have good dimensional stability. Compared to C-SPAEKS membrane (34.8 mS cm-1 at 20 °C, 109.8 mS cm-1 at 90 °C), the proton conductivities of C-SPAEKS/GO-0.75 membrane (52.4 mS cm-1 at 20 °C, 171.1 mS cm-1 at 90 °C) were significantly improved. Meanwhile, the C-SPAEKS/NGO-0.75 achieved peak power density of 407.77 mW cm-2 at high OCV of 0.9576 V. Such a result is much superior to the C-SPAEKS membrane (0.8973 V, 190.72 mW cm-2) and the Nafion 117 (0.99 V, 302 mW cm-2), and demonstrated good single-fuel cell performance. In summary, it can be well concluded that functionalized GO as filler makes an significant contribution in improving the overall performance of the composite membranes. • Functionalized GO containing amino group was synthesized. • An efficient and orderly proton transport channel was constructed. • The hybrid PEMs showed good proton conductivity (171.1 mS cm-1, at 90 °C). • The hybrid PEMs showed good single cell performance (407.77 mW cm-2, 80 °C, 100% RH). • Acid-base combination could improve proton conductivity effectively. [ABSTRACT FROM AUTHOR]

Positron emission tomography (PET) is becoming increasingly important in nuclear medicine and drug discovery. To date, the development of many potential PET tracers is hampered by the lack of suitable synthetic pathways for their preparation. This is particularly true for the highly desired radiolabeling of compounds bearing [18F]CF3‐groups. For instance, S(O)nCF3‐groups (n=0, 1, 2) serve as structural motif in a range of biologically active compounds, but their radiosynthesis remains largely unprecedented (for n=1, 2). Herein, we describe general methods for the radiosynthesis of 18F‐labeled aryl trifluoromethyl sulfones, ‐sulfoxides, and ‐sulfides. All three methods are operationally straightforward, start from widely available precursors, i.e., sulfonyl fluorides and thiophenols, and make use of the recently established [18F]Ruppert‐Prakash reagent. Further, the syntheses display good functional group tolerance as demonstrated by the 18F‐labeling of more than 40 compounds. The applicability of the new method is demonstrated by the radiolabeling of three bioactive molecules, optionally to be used as PET tracers. In a broader context, this work presents a substantial expansion of the chemical space of radiofluorinated structural motifs to be used for the development of new PET tracers. [ABSTRACT FROM AUTHOR]

A novel alkenylation reaction between N‐hydroxyphthalimide (NHPI) esters and alkenyl sulfones is reported. It undergoes the formation of electron donor‐acceptor (EDA) complex and a series of alkenes are obtained in good to excellent yields. It has the advantages of simple operation, mild reaction conditions, and metal‐free. [ABSTRACT FROM AUTHOR]

A visible-light induced selective oxidation of sulfides to sulfoxides or sulfones was reported at ambient temperature in H2O under catalyst-free conditions, using oxygen as a green oxidant. The surfactants play a key role in this oxidation, and sulfoxides or sulfones were obtained in high yields, respectively, promoted by different surfactants. [ABSTRACT FROM AUTHOR]

Despite their critical importance in drug development and biochemistry, efficiently synthesizing α-glycosyl azides has continued to pose significant challenges. In this report, we introduce a universal and practical radical reaction for the stereoselective synthesis of α-glycosyl azides using bench-stable allyl glycosyl sulfones as the donor. This method is characterized by its mild reaction conditions, high stereoselectivity, and extensive scope of glycosyl units. Moreover, the accessibility of several structurally complex drug–sugar conjugates underscores the practicality of our approach. [ABSTRACT FROM AUTHOR]

Membrane distillation is an emerging wastewater treatment technology that harnesses low-grade heat as an energy source and exhibits potential for complete desalination. Nonetheless, two notable challenges hinder the practical application of this technology: membrane wetting and fouling. To counter these challenges, an innovative anti-fouling Janus membrane with asymmetric wettability was developed through electrospinning. The hydrophobic layer was formed using tetraethyl orthosilicate/polysulfone (PSF), and the superhydrophilic layer was created using polyvinylpyrrolidone (PVP)/PSF. A sensitive adhesion probe was used to assess the anti-fouling performance of the Janus membrane against oil. Molecular dynamics simulation suggested that PVP reduced the adsorption tendency of the membrane for humic acid (HA). Under experimental conditions involving saline water with HA and a saline oil–water emulsion, the non-Janus membrane suffered severe fouling, resulting in rapid water permeate flux decline. However, the Janus membrane demonstrated consistent permeate flux (26.84 LMH and 24.92 LMH) and an impressive salt rejection rate (> 99.99%). This study suggests that the Janus membrane, with its high permeate fluxes and remarkable resistance to fouling and wetting, could be an effective solution for wastewater treatment, with considerable potential for future application. [ABSTRACT FROM AUTHOR]

Films with low dielectric constants have broad prospective applications in microelectronic devices. In this study, octavinyloctasilasesquioxane (POSS) was grafted with fluorinated long carbon chains on its eight vertices by clicking reaction. The successful synthesis of fluorinated POSS (F-POSS) was confirmed by NMR, FT-IR, and XPS analyses. Then, the F-POSS/poly (arylene sulfide sulfone) (F-POSS/PASS) composite films were fabricated via solution casting. When 15 wt.% of F-POSS was added, the dielectric constant of the F-POSS/PASS film at 1 MHz decreased from 3.52 to 2.65, while the Tan δ value dropped from 1.18*10–2 to 9.32*10–3, respectively. The developed F-POSS/PASS film showed excellent hydrophobicity (water contact angle of 120.3°) which was attributed to the fluorinated long carbon chains. In addition, the optimized F-POSS/PASS film also exhibited good mechanical properties (tensile strength 66.87 MPa), promising thermal stability, and flame-retardant property. Given the above-mentioned excellent properties, the F-POSS/PASS composite films will have great potential in the fabrication of microelectronic devices. [ABSTRACT FROM AUTHOR]

A terminal [NiII−OH] complex 1, supported by triflamide‐functionalized NHC ligands, showed divergent reactivity for the reaction of sulfone with alcohol, contingent on base concentration, temperature, and time. Julia‐type olefination of alcohols with sulfones was achieved using one equiv. of base, whereas lowering base loading to 0.5 equiv. afforded α‐alkylated sulfones. Besides excellent substrate scope and selectivity, biologically active stilbene derivatives DMU‐212, pinosylvin, resveratrol, and piceatannol were synthesized in high yield under Julia‐type olefination conditions. An extensive array of controlled experiments and DFT calculations provide valuable insight on the reaction pathway. [ABSTRACT FROM AUTHOR]

A one‐pot Pd‐catalyzed tandem process to prepare (2‐arylallyl) aryl sulfones has been developed. This strategy is based on the modular assembly of a boronic acid, a sodium sulfinate and 2‐bromoallyl acetate. The reaction is completely regioselective towards the terminal alkene, yielding (2‐arylallyl) aryl (or alkyl) sulfones with yields ranging from 56 to 93%. Control experiments together with DFT calculations allowed to propose a plausible reaction mechanism of the tandem reaction. The usefulness of this methodology has been demonstrated with the formal synthesis of the marketed drug Apremilast and of several natural products by asymmetric hydrogenation. Using the commercially available UbaPHOX iridium complex, chiral β‐methyl sulfones with up to 98% ee were obtained [ABSTRACT FROM AUTHOR]

Comprehensive Summary: The selective oxidative sulfonylation of alkenes with selenium sulfonate depended on the reaction conditions. The electrochemical C—H sulfonylation proceeded smoothly to afford (E)‐vinyl sulfones with good selectivity in an undivided cell without external oxidant. While aerobic trifunctionalization of alkenes occurred in the presence of KI in the air, which provides β‐keto selenosulfones via the formation of C—O, C—S, and C—Se bonds in one‐pot. Following control experiments, a plausible mechanism is proposed to rationalize the experimental results. [ABSTRACT FROM AUTHOR]

Synthetic efforts toward complex natural product (NP) scaffolds are useful ones, particularly those aimed at expanding their bioactive chemical space. Here, we utilised an orthogonal cheminformatics-based approach to predict the potential biological activities for a series of synthetic bis-indole alkaloids inspired by elusive sponge-derived NPs, echinosulfone A (1) and echinosulfonic acids A–D (2–5). Our work includes the first synthesis of desulfato-echinosulfonic acid C, an α-hydroxy bis(3′-indolyl) alkaloid (17), and its full NMR characterisation. This synthesis provides corroborating evidence for the structure revision of echinosulfonic acids A-C. Additionally, we demonstrate a robust synthetic strategy toward a diverse range of α-methine bis(3′-indolyl) acids and acetates (11–16) without the need for silica-based purification in either one or two steps. By integrating our synthetic library of bis-indoles with bioactivity data for 2048 marine indole alkaloids (reported up to the end of 2021), we analyzed their overlap with marine natural product chemical diversity. Notably, the C-6 dibrominated α-hydroxy bis(3′-indolyl) and α-methine bis(3′-indolyl) analogues (11, 14, and 17) were found to contain significant overlap with antibacterial C-6 dibrominated marine bis-indoles, guiding our biological evaluation. Validating the results of our cheminformatics analyses, the dibrominated α-methine bis(3′-indolyl) alkaloids (11, 12, 14, and 15) were found to exhibit antibacterial activities against methicillin-sensitive and -resistant Staphylococcus aureus. Further, while investigating other synthetic approaches toward bis-indole alkaloids, 16 incorrectly assigned synthetic α-hydroxy bis(3′-indolyl) alkaloids were identified. After careful analysis of their reported NMR data, and comparison with those obtained for the synthetic bis-indoles reported herein, all of the structures have been revised to α-methine bis(3′-indolyl) alkaloids. [ABSTRACT FROM AUTHOR]

Nine poly(phthalazinone ether ketone) resins were designed and synthesized using three bisphenol and four halogenated monomers. Poly(phthalazinone bisphenol ether ketone) (PPBEK) and poly(phthalazinone ether sulfone ketone) (PPBESK) demonstrated liquid oxygen compatibility (LOC), with PPBEK maintaining its LOC even after 20 days of immersion in liquid oxygen. The liquid oxygen compatibility mechanism of the polymers in the presence of force‐thermal‐chemical multi‐energy fields was analyzed using techniques such as thermal analysis‐infrared‐gas chromatography (TGA‐IR‐GC), thermogravimetric analysis (TGA), and x‐ray photoelectron spectroscopy (XPS). Carbon fiber (CF) reinforced composites were fabricated using PPBEK and PPBESK as matrices, with CF‐PPBEK composites successfully achieving LOC. The microcracking resistance and mechanical properties of the composites were investigated in liquid oxygen at 90 K. The interaction mechanism between the composites and liquid oxygen was elucidated, providing theoretical guidance and an experimental foundation for the application of resin matrix composites in liquid oxygen storage tanks. Highlights: Poly(phthalazinone ether) resins were meticulously designed and synthesized.·PPBEK and PPBESK exhibited excellent liquid oxygen compatibility.Composites exhibited excellent liquid oxygen compatibility.Composites exhibited excellent low‐temperature performance and heat resistance. [ABSTRACT FROM AUTHOR]

In the recent three decades, a steadily growing interest in the use of ball milling in organic synthesis has developed. The purpose of this mini-review is to briefly present protocols showing the use of ball milling in the formation and transformation of sulfur-containing functional groups. First, mechanochemical functionalization of sulfur-containing compounds is discussed. The second part devoted to interconversions of sulfur-containing functional groups in mechanochemical conditions summarizes the results on sulfenylation reactions, coupling reactions, redox reactions and condensation reactions. We hope that this review will be a useful addition to the collection of review publications devoted to mechanochemistry and will attract the attention of a wider group of researchers dealing with organosulfur chemistry by drawing attention to the attractive features of mechanochemical protocols. [ABSTRACT FROM AUTHOR]

Catalysts containing supported metal oxides are very versatile materials used in liquid phase oxidation reactions. The present study aimed to determine the influence of niobium supported on a silica matrix (SiO2) for the oxidation of thioanisole to methyl phenyl sulfoxide and methyl phenyl sulfone. Characterization of the synthesized Nb5SiO2 and Nb10SiO2 catalysts revealed that although they are not completely crystalline, these microporous materials displayed even niobium dispersion on the SiO2 support whilst containing Lewis and Brönsted acidic sites on their surface. Nb5SiO2 and Nb10SiO2 catalysts showed higher activities compared to pure SiO2 catalyst. Niobium-containing catalysts promoted the subsequent oxidation reaction that converted methyl phenyl sulfoxide to methyl phenyl sulfone. The formation of methyl phenyl sulfone was observed in the presence of niobium-containing catalysts even when using a deficiency of H2O2 (0.44 equivalents), whereas the same result could not be achieved for the SiO2 catalyst. The formation of methyl phenyl sulfone occurred in a significantly shorter time in the presence of Nb10SiO2, demonstrating the effectiveness of niobium in producing active oxygen species that promote the subsequent reactions. Under the optimized conditions, methyl phenyl sulfoxide could be obtained with 100% conversion and selectivity at room temperature (25 °C) in either acetonitrile or methanol as solvent. Finally, theoretical calculations showed, through energy values, that the niobium-containing catalysts have a lower relative surface energy compared to the pure silica catalyst. The results presented in this research show the potential of the synthesized materials to promote thioanisole catalytic oxidation reactions using hydrogen peroxide as an oxidant. [ABSTRACT FROM AUTHOR]

Large amount of energy is being contemporarily expended in carrying out separation and purification operations via thermodynamically inefficient conventional processes. Membrane-based separation technology has recently gained much attractiveness owing to its energy efficient process, reliable operation, low maintenance requirements, economical effectiveness, molecularly selective separation, and compact designing. Highly permeable and selective polymer-based flat-sheet polyether sulfone-based membranes were prepared followed by their insertion into compact spiral-wound modules for efficient carbon capture in this work. Carbon capture efficiency of prepared membranes and corresponding modules was evaluated by trialing them under various operating conditions on a custom-built laboratory-scale rig. Impact of precipitation technique and temperature on carbon capture capacity of resulting membranes and modules can be comprehended by precipitating cast films either through solvent evaporation or water submersion at two distinct temperatures of 5 and 20 °C. CO2 permeability of water-immersed membrane having 57 Barrer was uplifted to 61 Barrer for solvent-evaporated membrane. CO2/N2 selectivity of water-precipitated membrane was improved from 6 to 11 by precipitating at 5 °C instead of 20 °C. Flexible and frail properties of water-precipitated amorphous membranes can be turned into robust and relatively rigid semi-crystalline films owing to solvent evaporation. [ABSTRACT FROM AUTHOR]

Hydrofunctionalization is one of the most important transformation reactions of alkenes which allows for rapid increase in molecular complexity by installing functional groups across the carbon–carbon double bonds. In this context, over the past few years, the experimental synthesis of biologically important aliphatic sulfones through the hydrosulfonylation of olefinic double bonds has attracted tremendous attention due to its straightforward manner with high atom- and step-economy, and also easily accessible starting materials. The aim of the present paper is to perform a review of recent advances made on this research topic, with special emphasis on the mechanistic aspect of the reactions. [ABSTRACT FROM AUTHOR]

The solar‐driven photocatalytic production of hydrogen peroxide (H2O2) from water and oxygen using semiconductor catalysts offers a promising approach for converting solar energy into storable chemical energy. However, the efficiency of photocatalytic H2O2 production is often restricted by the low photo‐generated charge separation, slow surface reactions and inadequate stability. Here, we developed a mixed‐linker strategy to build a donor‐acceptor‐acceptor (D–A–A) type covalent organic framework (COF) photocatalyst, FS‐OHOMe‐COF. The FS‐OHOMe‐COF structure features extended π–π conjugation that improves charge mobility, while the introduction of sulfone units not only as active sites facilitates surface reactions with water but also bolsters stability through increased interlayer forces. The resulting FS‐OHOMe‐COF has a low exciton binding energy, long excited‐state lifetime and high photo‐stability that leads to high performance for photocatalytic H2O2 production (up to 1.0 mM h−1) with an H2O2 output of 19 mM after 72 hours of irradiation. Furthermore, the catalyst demonstrates high stability, which sustained activity over 192 hours of photocatalytic experiment. [ABSTRACT FROM AUTHOR]

Ligand coupling on hypervalent main group elements has emerged as a pivotal methodology for the synthesis of functionalized N‐heteroaromatic compounds in recent years due to the avoidance of transition metals and the mildness of the reaction conditions. In this direction, the reaction of N‐heteroaryl sulfur(IV) and N‐heteroaryl phosphorus(V) compounds has been well studied. However, the ligand coupling of sulfur(VI) is still underdeveloped and the reaction of alkyl N‐heteroarylsulfones is still elusive, which does not match the high status of sulfones as the chemical chameleons in organic synthesis. Here we present a ligand coupling‐enabled formal SO2 extrusion of fluoroalkyl 2‐azaheteroarylsulfones under the promotion of Grignard reagents, which not only enriches the chemistry of sulfones, but also provides a novel and practical synthetic tool towards N‐heteroaromatic fluoroalkylation. [ABSTRACT FROM AUTHOR]

The first assortment of achiral pentafluorosulfanylated cyclobutanes (SF5‐CBs) are now synthetically accessible through strain‐release functionalization of [1.1.0]bicyclobutanes (BCBs) using SF5Cl. Methods for both chloropentafluorosulfanylation and hydropentafluorosulfanylation of sulfone‐based BCBs are detailed herein, as well as proof‐of‐concept that the logic extends to tetrafluoro(aryl)sulfanylation, tetrafluoro(trifluoromethyl)sulfanylation, and three‐component pentafluorosulfanylation reactions. The methods presented enable isolation of both syn and anti isomers of SF5‐CBs, but we also demonstrate that this innate selectivity can be overridden in chloropentafluorosulfanylation; that is, an anti‐stereoselective variant of SF5Cl addition across sulfone‐based BCBs can be achieved by using inexpensive copper salt additives. Considering the SF5 group and CBs have been employed individually as nonclassical bioisosteres, structural aspects of these unique SF5‐CB "hybrid isosteres" were then contextualized using SC‐XRD. From a mechanistic standpoint, chloropentafluorosulfanylation ostensibly proceeds through a curious polarity mismatch addition of electrophilic SF5 radicals to the electrophilic sites of the BCBs. Upon examining carbonyl‐containing BCBs, we also observed rare instances whereby radical addition to the 1‐position of a BCB occurs. The nature of the key C(sp3)−SF5 bond formation step – among other mechanistic features of the methods we disclose – was investigated experimentally and with DFT calculations. Lastly, we demonstrate compatibility of SF5‐CBs with various downstream functionalizations. [ABSTRACT FROM AUTHOR]