Search

The sulfinyl group, as one of the bioisosteres of carbonyl groups, attracts considerable attention in the field of synthetic chemistry. In particular, the asymmetric construction of chiral sulfinyl compounds and their derivatives remains in the early stages of development. Sulfinyl compounds mainly include sulfoxides, sulfinate esters and sulfinamides, according to the different functional groups connected to the sulfur atom. This Review summarizes the fascinating recent progress made over the past decade on the asymmetric synthesis of enantiopure sulfinyl derivatives. 1 Introduction 2 Asymmetric Synthesis of Chiral Sulfoxides 3 Asymmetric Synthesis of Chiral Sulfinate Esters 4 Asymmetric Synthesis of Chiral Sulfinamides 5 Conclusion and Outlook [ABSTRACT FROM AUTHOR]

Access to original ortho thioether derivatives was achieved through a [3,3]-rearrangement in a one-pot two-step protocol. Several aryl-SCF3 compounds are reported by variation of the nitrile or of the trifluoroalkyl sulfoxide starting material. The variation of the perfluoroalkyl chain was also possible.

Abstract In this research project, a versatile procedure has been designed for the preparation of supported copper@curcumin on magnetic graphene oxide nanoparticles (GO@Fe3O4@Cur–Cu). The structure of prepared nanocatalyst was characterized by several techniques including; Fourier transform infrared, powder X-ray diffraction, thermal gravimetric analysis, energy dispersive X-ray analysis, inductively coupled plasma optical emission spectroscopy, vibrating sample magnetometer, transmission electron microscopy, and scanning electron microscopy analyses. The catalytic properties of GO@Fe3O4@Cur–Cu were examined for the efficient synthesis of polyhydroquinolines as well as the preparation of sulfoxides through selective oxidation of sulfides in the presence of hydrogen peroxide.

The synthesis of sulfoxide‐functionalized NHC ligand precursors were carried out by direct and mild oxidation from corresponding thioether precursors with high selectivity. Using these salts, a series of cationic [Ru(II)(η6‐p‐cymene)(NHC‐SO)Cl]+ complexes were obtained in excellent yields by the classical Ag2O transmetallation route. NMR analyses suggested a chelate structure for the metal complexes, and X‐ray diffractometry studies of complexes 4 b, 4 c, 4dBArF and 4 e unambiguously confirmed the preference for the bidentate (κ2‐C,S) coordination mode of the NHC‐SO ligands. Interestingly, only one diastereomer, in the form of an enantiomeric pair, was observed both in 1H NMR and in the solid state for the complexes. DFT calculations showed a possible intrinsic energy difference between the two pairs of diastereomer. The calculated energy barriers suggested that inversion of the sulfoxide is only plausible from the higher energy diastereomer together with bulky substituents. Inverting the configuration at the Ru center instead shows a lower and accessible activation barrier to provide the most stable diastereomer through thermodynamic control, consistent with the observation of a single species by 1H NMR as a pair of enantiomers. All these complexes catalyse the β‐alkylation of secondary alcohols. Complex 4dPF6 bearing an NHC‐functionalised S‐Ad group has been further studied with different primary and secondary alcohols as substrates, showing high reactivity and high to moderate β‐ol‐selectivities. [ABSTRACT FROM AUTHOR]

In this research project, a versatile procedure has been designed for the preparation of supported copper@curcumin on magnetic graphene oxide nanoparticles (GO@Fe3O4@Cur–Cu). The structure of prepared nanocatalyst was characterized by several techniques including; Fourier transform infrared, powder X-ray diffraction, thermal gravimetric analysis, energy dispersive X-ray analysis, inductively coupled plasma optical emission spectroscopy, vibrating sample magnetometer, transmission electron microscopy, and scanning electron microscopy analyses. The catalytic properties of GO@Fe3O4@Cur–Cu were examined for the efficient synthesis of polyhydroquinolines as well as the preparation of sulfoxides through selective oxidation of sulfides in the presence of hydrogen peroxide. [ABSTRACT FROM AUTHOR]

A transition‐metal‐free protocol is proposed for the selective oxidation of flavones, providing various sulfoxide/sulfone‐flavonoids in excellent yields. This strategy features excellent selectivities, high yields and broad substrate scope. The combination of oxone (2KHSO5 ⋅ KHSO 4⋅ K2SO4) as the sole oxidant and NaHCO3/Na2CO3 as the buffer play an important role in the process, in which the amounts of oxone and reaction temperatures are the key to the outstanding selectivities and high efficiency of the reaction. It should be noteworthy that a class of novel sulfone‐flavonols is also synthesized through triple oxidation. Moreover, the glycosylation of sulfone‐flavonols has been realized. [ABSTRACT FROM AUTHOR]

This article explores the use of bicyclopentane (BCP) as a bioisostere in medicinal chemistry. BCP can replace phenyl rings or alkynes in molecules, altering their physical properties. The authors focus on the synthesis of BCP-sulfoxides, which can enhance the pharmacological properties of compounds. They present a new method using a BCP-sulfinate precursor that is more convenient and stable. The authors successfully synthesized a previously inaccessible methyl-substituted sulfoxide and suggest the potential for further modifications. [Extracted from the article]

Abstract Iron nanoparticles, with low toxicity and many active sites, are among the materials that not only reduce waste along with green chemistry but also increase the separation power and recover the catalyst from the reaction environment. In this study, first, the surface of iron nanoparticles was silanized, and in the next step, the complex of chitosan HCl.VO3 was placed on the surface of Fe3O4 (Fe3O4@SiO2@CSH+VO3 −). This nanocatalyst is a novel, recoverable, and potent nanocatalyst with high selectivity for the oxidation of sulfides to sulfoxides. Various physicochemical techniques such as IR, XRD, TGA, SEM, EDX, mapping, TEM, and VSM were used to affirm the well synthesis of the catalyst. Oxidation of sulfides in the presence of hydrogen peroxide as a green oxidant and in ethanol was catalyzed by the Fe3O4@SiO2@CSH+VO3 −. All sulfoxides were achieved with high efficiency and in a short time. The notable privileges of this method include facile and economic catalyst synthesis, proper catalyst durability, great performance, simple catalyst isolation, good recovery capability, at least up to 5 times without an index drop in catalytic power.

Abstract Herein, we report the synthesis of ZnFe2O4@SiO2@L-lysine@SO3H as a green, novel magnetic nanocatalyst, containing the sulfuric acid catalytic sites on the surface of zinc ferrite as the catalytic support. The physical and chemical properties of raw and modified samples (ZnFe2O4@SiO2@L-lysine@SO3H) were characterized by TGA, EDX, PXRD, Map, and FTIR analyses. The prepared nanocatalyst has excellent catalytic activity in synthesizing the oxidation of sulfides to the sulfoxides and Synthesis of pyrazolyl (Bis(pyrazolyl)methane) derivatives under green conditions. This designed nanocatalyst offers several advantages including the use of inexpensive materials and high yield, simple procedure, and commercially available. The synthesized mesoporous nanocatalyst was recovered and reused in five continuous cycles without considerable change in its catalytic activity.

The absolute configuration and stability of two thianthrene chiral sulfoxides has been determined by means of X-ray single-crystal structure determinations. The analyses and configurations allow verification that the diastereomeric sulfoxides are stable in solution and are not interconverting, which has been suggested in some studies of sulfoxides. The two thianthrene sulfoxides have slightly different Rf values, which allowed their separation using flash chromatography on silica. The spots run back-to-back, which posed a challenge for their separation. The pure, separated compounds in solution remain as separate, single spots on a Thin Layer Chromatography (TLC) plate. [ABSTRACT FROM AUTHOR]

Iron nanoparticles, with low toxicity and many active sites, are among the materials that not only reduce waste along with green chemistry but also increase the separation power and recover the catalyst from the reaction environment. In this study, first, the surface of iron nanoparticles was silanized, and in the next step, the complex of chitosan HCl.VO3 was placed on the surface of Fe3O4 (Fe3O4@SiO2@CSH+VO3−). This nanocatalyst is a novel, recoverable, and potent nanocatalyst with high selectivity for the oxidation of sulfides to sulfoxides. Various physicochemical techniques such as IR, XRD, TGA, SEM, EDX, mapping, TEM, and VSM were used to affirm the well synthesis of the catalyst. Oxidation of sulfides in the presence of hydrogen peroxide as a green oxidant and in ethanol was catalyzed by the Fe3O4@SiO2@CSH+VO3−. All sulfoxides were achieved with high efficiency and in a short time. The notable privileges of this method include facile and economic catalyst synthesis, proper catalyst durability, great performance, simple catalyst isolation, good recovery capability, at least up to 5 times without an index drop in catalytic power. [ABSTRACT FROM AUTHOR]

Organic molecules containing fluorine and sulfur atoms represent a large percentage of approved pharmaceuticals. Those with combination of both S and F atoms in their structure such as Xtandi, approved in 2012 for prostate cancer, indicates the importance of synthetic methods that accommodates both atoms in an organic moiety. In this study, a novel aspect of sulfoxonium ylide reactivity was explored, unveiling a streamlined and mild synthesis method for gem‐difluorinated keto‐sulfoxides. Our protocol offers a direct and practical approach to prepare these compounds in 14–80 % chemical yields, that were represented by 21 examples. NMR studies and Hammett correlations gave strong evidence about the mechanism of this transformation. [ABSTRACT FROM AUTHOR]

2,6-Diaryl-4H-tetrahydro-thiopyran-4-ones and corresponding sulfoxide and sulfone derivatives were designed to lower the major toxicity of their parent anti-kinetoplatidal diarylideneacetones through a prodrug effect. Novel diastereoselective methodologies were developed and generalized from diarylideneacetones and 2,6-diaryl-4H-tetrahydro-thiopyran-4-ones to allow the introduction of a wide substitution profile and to prepare the related S-oxides. The in vitro biological activity and selectivity of diarylideneacetones, 2,6-diaryl-4H-tetrahydro-thiopyran-4-ones, and their S-sulfoxide and sulfone metabolites were evaluated against Trypanosoma brucei brucei, Trypanosoma cruzi, and various Leishmania species in comparison with their cytotoxicity against human fibroblasts hMRC-5. The data revealed that the sulfides, sulfoxides, and sulfones, in which the Michael acceptor sites are temporarily masked, are less toxic against mammal cells while the anti-trypanosomal potency was maintained against T. b. brucei, T. cruzi, L. infantum, and L. donovani, thus confirming the validity of the prodrug strategy. The mechanism of action is proposed to be due to the involvement of diarylideneacetones in cascades of redox reactions involving the trypanothione system. After Michael addition of the dithiol to the double bonds, resulting in an elongated polymer, the latter—upon S-oxidation, followed by syn-eliminations—fragments, under continuous release of reactive oxygen species and sulfenic/sulfonic species, causing the death of the trypanosomal parasites in the micromolar or submicromolar range with high selectivity indexes. [ABSTRACT FROM AUTHOR]

In this project, the l-arginine salen Schiff-base (ASS) complex of lanthanum on the functionalized surface of mesoporous MCM-41 (MCM-41@ASS-La) was synthesized for the first time. To prepare MCM-41@ASS-La, the surface of MCM-41 was modified with 3-iodopropyl trimethoxysilane (IPTMS) and then l-arginine salen Schiff-base ligand anchored om modified MCM-41. Then, lanthanum ions were stabilized on its surface. Then, MCM-41@ASS-La was characterized by different techniques e.g. Fourier transform infrared spectroscopy (FTIR), energy-dispersive X-ray Spectroscopy (EDX), scanning electron microscopy (SEM), wavelength dispersive X-ray spectroscopy (WDX), energy-dispersive X-ray spectroscopy (EDS), inductively coupled plasma atomic emission spectroscopy (ICP-AES), and N2 adsorption–desorption isotherms. Next step, the synthesized MCM-41@ASS-La was investigated as an efficient and reusable nanocatalyst for the chemoselective synthesis of sulfoxides and tetrahydrobenzo[b]pyrans. In these studies, the reaction conditions for the synthesis of tetrahydrobenzo[b]pyrans were optimized, and the best results were obtained in H2O as an ideal, available and, green solvent in the presence of MCM-41@ASS-La nanocatalyst. Also, the reaction conditions for the oxidation of sulfides to sulfoxides were optimized, and the best results were obtained under solvent-free conditions using hydrogen peroxide (H2O2) in the presence of MCM-41@ASS-La nanocatalyst. Then, several derivatives of sulfoxides and tetrahydrobenzo[b]pyrans were synthesized in the presence of MCM-41@ASS-La nanocatalyst under optimized conditions. In addition, MCM-41@ASS-La nanocatalyst can be recovered (about 96%) and reused for several cycles without metal leaching or reactivation. [ABSTRACT FROM AUTHOR]

In this work, a new Ni(II) unsymmetrical Schiff-base complex, Ni(salenac), was successfully synthesized and immobilized into three-dimensional (3D) mesoporous silica KIT-6 (Korean Institute of Technology No. 6). The novel composite KIT-6-pr-NH2-Ni(salenac) was characterized by various techniques and utilized to selectively oxidize different aromatic and aliphatic sulfides to the corresponding sulfoxides with yields of 80–95% by using hydrogen peroxide (30% H2O2) as an environmentally friendly oxidant in ethanol solution at 25 °C. This oxidizing system allowed the chemoselective oxidation of sulfides containing other functional groups. The results showed that the OH and C=C groups of the compounds such as 2-hydroxyethyl phenyl sulfide and allyl methyl sulfide remained intact during sulfide oxidation. The catalyst was stable in the reaction conditions, and could be recused at least five times without significant decline in catalytic activity. Moreover, Fourier transform infrared (FTIR) spectrum of the recovered catalyst matches that of the fresh catalyst, and the catalyst structure remains unchanged after recovery. [ABSTRACT FROM AUTHOR]

Herein, we report the synthesis of ZnFe2O4@SiO2@L-lysine@SO3H as a green, novel magnetic nanocatalyst, containing the sulfuric acid catalytic sites on the surface of zinc ferrite as the catalytic support. The physical and chemical properties of raw and modified samples (ZnFe2O4@SiO2@L-lysine@SO3H) were characterized by TGA, EDX, PXRD, Map, and FTIR analyses. The prepared nanocatalyst has excellent catalytic activity in synthesizing the oxidation of sulfides to the sulfoxides and Synthesis of pyrazolyl (Bis(pyrazolyl)methane) derivatives under green conditions. This designed nanocatalyst offers several advantages including the use of inexpensive materials and high yield, simple procedure, and commercially available. The synthesized mesoporous nanocatalyst was recovered and reused in five continuous cycles without considerable change in its catalytic activity. [ABSTRACT FROM AUTHOR]

The aerobic photooxidation of sulfides into sulfoxides in eco-friendly solvents, notably water, at room temperature, represents a significant interest in the domain of synthetic chemistry. This study introduces four highly stable hexadentate Ir(III) complexes: [Ir(fpqen)](PF6) (1), [Ir(btqen)](PF6) (2), [Ir(bmpqen)](PF6) (3), and [Ir(bnqen](PF6) (4) (where bfpqen is N,N′-bis(2-(4-fluorophenyl)quinolin-8-yl)ethane-1,2-diamine, btqen is N,N′-bis(2-(4-tolyl)quinolin-8-yl)ethane-1,2-diamine, bmpqen is N,N′-bis(2-(4-methoxyphenyl)quinolin-8-yl)ethane-1,2-diamine, and bnqen is N,N′-bis(2-naphthylquinolin-8-yl)ethane-1,2-diamine). These complexes were synthesized utilizing an in situ inter-ligand C-N cross-coupling photoreaction of the precursors [Ir(L)2(en)](PF6) (L is 2-(4-fluorophenyl)quinoline, (2-(4-tolyl)quinoline, 2-(4-methoxyphenyl)quinoline or 2-naphthylquinoline, and en is 1,2-diamine) under benign conditions. This methodology furnishes a valuable and complementary approach for the in situ generation of multidentate complexes through a post-coordination inter-ligand-coupling strategy under mild conditions. Moreover, these hexadentate Ir(III) complexes exhibit pronounced catalytic activity and chemo-selectivity toward the aerobic photooxidations of sulfides into sulfoxides in aqueous media at room temperature, offering a new avenue for the sustainable synthesis of sulfoxides. [ABSTRACT FROM AUTHOR]

We report herein an unprecedented hypervalent iodine(III)‐catalysis using the activated sulfoxide. Since the present catalytic systems promote the dehydrogenative cycloisomerization‐arylation reaction of 2‐propargyl 1,3‐dicarbonyl compounds with aromatics, this report also provides one of the few methods for iodine(III)‐catalyzed intermolecular carbon‐carbon bond formation of aromatics. [ABSTRACT FROM AUTHOR]

Two sulfoxide-containing Schiff bases, (E)-(((2-(methylsulfinyl phenyl) imino)methyl)-4-nitrophenol (HL1) and (E)-3,5-dibromo-2-(((2-(methylsulfinyl phenyl)imino)methyl)phenol (HL2), were prepared by condensation and subsequent oxidation reactions. In the presence of triethylamine, reactions of HL1 with 0.5 equivalent of copper acetate, cobalt acetate, nickel acetate and zinc acetate in ethanol afforded four metal complexes: (η2-N,O-L1)Cu(η3-O,N,O-L1) (1) and (η3-O,N,O-L1)2M (M = Co, 2; Ni, 3; Zn, 4), respectively. Similarly, treatment of HL2 with 0.5 equivalent of cobalt acetate and nickel acetate obtained two cobalt/nickel complexes: (η3-O,N,O-L2)2M (M = Co, 5; Ni, 6). Reactions of HL1 and one equivalent of Ru(PPh3)3Cl2 in tetrahydrofuran in the presence of triethylamine afforded a ruthenium(II) complex, (η3-O,N,S-L1)Ru(PPh3)2Cl (7). The molecular structures of HL1 and 1-7 have been confirmed by single-crystal X-ray diffraction. In addition, the UV–Vis, infrared, and fluorescence spectroscopies of 1–7 along with their electrochemical properties were also investigated. [ABSTRACT FROM AUTHOR]

Six series of benzoheterocyclic sulfoxide derivatives were designed and synthesised as Pseudomonas aeruginosa (P. aeruginosa) quorum sensing inhibitors in this paper. We experimentally demonstrated that 6b significantly inhibited the formation of P. aeruginosa PAO1 biofilm without affecting the growth. Further mechanistic studies showed that 6b affected the luminescence of quorum sensing reported strain PAO1-lasB-gfp and the production of P. aeruginosa PAO1 elastase virulence factor which was regulated by las system. These experimental results indicate that 6b acts as a quorum sensing inhibitor mainly through the las system. Furthermore, silico molecular docking studies demonstrated that 6b and the P. aeruginosa quorum sensing receptor LasR were molecularly bound via hydrogen bonding interactions. Preliminary structure-activity relationship and docking studies illustrated that 6b shows great promise as anti-biofilm compounds for further studies in order to solve the problem of microbial resistance in future. [ABSTRACT FROM AUTHOR]

The purpose of the research is to study the biotransformation of fenbendazole in the body of sheep after administration of fenbendazole solid dispersion (FSD) prepared by mechanochemical technique with arabinogalactan. Materials and methods. The FSD at a dose of 2.0 mg/kg for the active substance was administered orally to sheep. Animal blood serum samples were studied by high performance liquid chromatography / tandem mass spectrometry (HPLC-TMS) to determine the concentration of fenbendazole (FBZ) and its sulfoxide and sulfone metabolites at 0, 1, 2, 4, 6, 8, 12, 24, 33, 48 and 72 hours after administered FSD and initial FBZ (substance). FBZ and its metabolite residual quantity in the organs and tissues of the sheep was determined at 1, 3, 6, 11, and 21 days after the drug administration. The prepared sample and validated method were described. Results and discussion. A significant difference was found in the metabolism, pharmacokinetics, and timing of the FBZ and its metabolite elimination after the base drug (FBZ substance) and FSD were administered to sheep in an equal dose of 2.0 mg/kg for the active substance. FBZ and its metabolites began to be detected in blood serum 2 hours after the FSD and 4 hours after the base FBZ. Pharmacokinetic parameters of FBZ and its metabolites characterize a higher drug concentration in the blood and a longer retention time in the circulation after the FSD as compared with the base drug parameters. The FBZ and its metabolite maximum concentration was found in the organs and tissues of the sheep that received the FSD on day 3 in the liver amount of 4862.3±296.2 ng/g of FBZ; 18243.5±486.1 ng/g of sulfoxide; and 2482.3±132.4 ng/g of sulfone; and tens of times lower concentration after the base FBZ on day 6. FBZ and its metabolites were not detected in the organs and tissues of the sheep on day 16 after the base FBZ, and on day 21 after the FSD.

Abstract The escalating demand for effective and sustainable weed management strategies, driven by urbanization expansion, is a critical challenge. Herbicides are pivotal tools in modern agriculture, addressing this challenge. Developing novel herbicides with enhanced efficacy and minimal environmental impact is crucial for food security and ecological balance. While numerous herbicides have been developed with varying availability over time and regions, there's a continuous need for innovation. In this study, we explored relatively understudied sulfoxide-containing herbicides and synthesized a smaller yet substantial sulfoxide scaffold for herbicide development. Through screening Digitaria ciliaris (Retz.) Koeler, Amaranthus lividus L., and Solanum nigrum L., we observed promising herbicidal efficacy, especially against Wild Amaranth. Encouraged by preliminary findings, we recognize the potential for refining the core structure. In summary, we fashioned a structurally simple sulfoxide scaffold showcasing discernible herbicidal impact on broadleaf weeds.

The activation of C-H bonds is a potent tool for modifying molecular structures in chemistry. This article details the steps involved in a novel ligand bearing a bicyclic [3.3.1]-nonane framework and bissulfoxide moiety. A palladium catalyzed allylic C-H oxidation method enables a direct benzyl-allylic functionalization with the bissulfoxide ligand. Bissulfoixde ligand possesses a rapidly constructed bicyclic [3.3.1] framework and it proved to be effective for enabling both N- and C-alkylation. A total of 13 C-H activation productions were reported with good to excellent yields. This report validated that it is necessary to include bissulfoxide as a ligand for superior reactivities. Naftifine was produced utilizing developed C-H functionalization methodology in good overall yields.

Six series of benzoheterocyclic sulfoxide derivatives were designed and synthesised as Pseudomonas aeruginosa (P. aeruginosa) quorum sensing inhibitors in this paper. We experimentally demonstrated that 6b significantly inhibited the formation of P. aeruginosa PAO1 biofilm without affecting the growth. Further mechanistic studies showed that 6b affected the luminescence of quorum sensing reported strain PAO1-lasB-gfp and the production of P. aeruginosa PAO1 elastase virulence factor which was regulated by las system. These experimental results indicate that 6b acts as a quorum sensing inhibitor mainly through the las system. Furthermore, silico molecular docking studies demonstrated that 6b and the P. aeruginosa quorum sensing receptor LasR were molecularly bound via hydrogen bonding interactions. Preliminary structure-activity relationship and docking studies illustrated that 6b shows great promise as anti-biofilm compounds for further studies in order to solve the problem of microbial resistance in future.

A rapid synthesis of chiral sulfoxide-functionalized meta-terphenyl derivatives by a 2,5-[C4+C2] ring transformation reaction of pyrylium salts with in situ generated enantiomerically pure α-sulfinylacetaldehydes is described in this paper. This synthetic method demonstrates, for the first time, the use of α-sulfinylacetaldehydes in a reaction sequence initiated by the nucleophilic attack of pyrylium salts by α-sulfinylcarbanions to generate chiral aromatic systems. The method presented shows a broad applicability starting with various methyl sulfoxides and a number of functionalized pyrylium salts, furnishing meta-terphenyls with complex substitution patterns from readily accessible starting compounds. [ABSTRACT FROM AUTHOR]

C-aryl glycosides are an important kind of carbohydrate derivatives for drug discovery, due to their distinctive attributes of resistance to hydrolysis from enzymes. Herein, C-aryl glycosylation was established for the synthesis of 2-sulfur C-aryl glycals and 1,2-dihydrobenzofuran-fused C-aryl glycosides via interrupted Pummerer process, featured with sulfonium-tethered [3,3]-sigmatropic rearrangement between sulfoxide glycals and phenols. This protocol offers a broad substrate scope with diverse glycosyl and phenols. Dapagliflozin, Empagliflozin, and Ipragliflozin analogs were straightforward achieved, respectively. [ABSTRACT FROM AUTHOR]

The escalating demand for effective and sustainable weed management strategies, driven by urbanization expansion, is a critical challenge. Herbicides are pivotal tools in modern agriculture, addressing this challenge. Developing novel herbicides with enhanced efficacy and minimal environmental impact is crucial for food security and ecological balance. While numerous herbicides have been developed with varying availability over time and regions, there's a continuous need for innovation. In this study, we explored relatively understudied sulfoxide-containing herbicides and synthesized a smaller yet substantial sulfoxide scaffold for herbicide development. Through screening Digitaria ciliaris (Retz.) Koeler, Amaranthus lividus L., and Solanum nigrum L., we observed promising herbicidal efficacy, especially against Wild Amaranth. Encouraged by preliminary findings, we recognize the potential for refining the core structure. In summary, we fashioned a structurally simple sulfoxide scaffold showcasing discernible herbicidal impact on broadleaf weeds. [ABSTRACT FROM AUTHOR]

Oxidation of 4-[(alkylsulfanyl)methyl]-3,5-dimethylisoxazoles with 1,1-di(hydroperoxy)-cyclohexane in benzene or ethanol under mild conditions gave the corresponding 4-[(alkyl-sulfinyl)methyl]-3,5-dimethylisoxazoles in up to 99% yields. [ABSTRACT FROM AUTHOR]

Herein we designed a strategy for the synthesis of regioselective and stereoselective displacement of C‐3 acetate group in the presence of other C‐4 and C‐6 acetate of 2‐ketophenyl‐glycal by different aromatic and cyclic aliphatic thiol nucleophiles taking inspiration from cytosolic esterase mediated thiolation of glucosamine sugars into cellular glycan. Under a mild base condition at room temperature, the protocol generated a library of 3‐arylthiosugars with excellent yields and high axial selectivity. This stereoselective approach tolerated well with different ester‐protected glycals and thiophenols, aliphatic cyclic thiols, and mercaptans. A variety of control experiments were conducted to establish the mechanism and reason behind the stereoselectivity. [ABSTRACT FROM AUTHOR]

The absolute configuration and stability of two thianthrene chiral sulfoxides has been determined by means of X-ray single-crystal structure determinations. The analyses and configurations allow verification that the diastereomeric sulfoxides are stable in solution and are not interconverting, which has been suggested in some studies of sulfoxides. The two thianthrene sulfoxides have slightly different Rf values, which allowed their separation using flash chromatography on silica. The spots run back-to-back, which posed a challenge for their separation. The pure, separated compounds in solution remain as separate, single spots on a Thin Layer Chromatography (TLC) plate.

Fenbendazole (FBZ) is one of the most widely used drugs in veterinary medicine. Modification of its physicochemical properties, in particular the parameter of solubility, contributes to a change in its biological activity, which is shown on the model of trichinellosis of white mice. An analysis of methods of obtaining new preparations of fenbendazole is presented: solid dispersions of fenbendazole with polymers, as well as combinations with polymers and succinic acid (SA) and mixed crystals of FBZ with SA. The concentration of the active substance, the stability, and the effect on biological activity were studied. [ABSTRACT FROM AUTHOR]

Phytochemical investigation of the seeds of Capsella bursa-pastoris led to the isolation of four organosulfur compounds. There were two new compounds, 10-methylsulfinyl-decanamide (1) and 11-methylsulfinyl-undecanamide (2), along with two known compounds (3 − 4), which all have a sulfoxide group and an amide or a nitrile group. Their chemical structures were elucidated by analysing UV, IR, ESI-MS and NMR spectroscopy. In addition, compounds 1 − 4 were evaluated for their anti-inflammatory activities by using LPS-induced RAW 264.7 cells. Compounds 1 − 4 exhibited potential anti-inflammatory activities on NO release characterised by decreasing the mRNA expression levels of inducible NO synthase (iNOS), cytokines cyclooxygenase-2 (COX-2) and interleukin 6 (IL-6). [ABSTRACT FROM AUTHOR]

Benzothiophenes, activated by oxidation to the corresponding S‐oxides, undergo C−H/C−H‐type coupling with phenols to give C4 arylation products. While an electron‐withdrawing group at C3 of the benzothiophene is important, the process operates without a directing group and a metal catalyst, thus rendering it compatible with sensitive functionalities—e.g. halides and formyl groups. Quantum chemical calculations suggest a formal stepwise mechanism involving heterolytic cleavage of an aryloxysulfur species to give a π‐complex of the corresponding benzothiophene and a phenoxonium cation. Subsequent addition of the phenoxonium cation to the C4 position of the benzothiophene is favored over the addition to C3; Fukui functions predict that the major regioisomer is formed at the more electron‐rich position between C3 and C4. Varied selective manipulation of the benzothiophene products showcase the synthetic utility of the metal‐free arylation process. [ABSTRACT FROM AUTHOR]

The simple synthesis of NaY, Ni-NaY, and Mn-NaY zeolites nanoparticles was investigated and developed for utilization as efficient catalysts for the oxidation of sulfides to sulfoxides after characterization of the catalyst by XRD, SEM, TGA-DTA, and EDS techniques. The chemical formula of the samples was determined as NaY (Na0.91AlSi2.31O11), NiNaY (Ni0.64Na0.15AlSi2.3O11), and MnNaY (Mn0.5Na0.15AlSi2.3O11) using the EDS analysis. The prepared catalyst has suitable potential for the oxidation of sulfides to sulfoxides under mild conditions and was reused 11 times without significant losses in its potential and catalytic activity. [ABSTRACT FROM AUTHOR]

With the instability and alternative reactive modes of alkyl sulfenyl chlorides making the synthesis of a broad range of alkyl allenyl sulfoxides via the [2,3]-sigmatropic rearrangement difficult, alternative sources of electrophilic sulfur were explored. Examination of various N-sulfanylimides revealed that thiosuccinimides are a viable sulfur source for the synthesis of alkyl allenyl sulfoxides via the [2,3]-sigmatropic rearrangement. With the optimized conditions of excess propargyl alcohol and potassium carbonate in chloroform at 50 °C, a variety of alkyl allenyl sulfoxides were synthesized in fair to good yields (21–73%, 21 examples). Additionally, butyn-1,4-diols can be selectively monofunctionalized with a large excess of diol and stoichiometric triethylamine in THF at room temperature to form 1-hydroxyalkyl allenyl sulfoxides (26–71%). These diols can also be bis-functionalized to form 2,3-disubstitued dienes (53–66%) via two separate [2,3]-sigmatropic rearrangements. The formation of alkyl allenyl sulfoxides was also found to be selective for less substitution at the propargyl position (3:1–100:0 ratio) as shown in direct competition experiments. Trimethylsilylethyl thiosuccinimides were among the highest yielding of the thioimides. The sulfenate chemistry of select allenyl sulfoxides can be successfully performed. [ABSTRACT FROM AUTHOR]

Sulfenate anions (RSO-M+) represent emerging sulfur nucleophiles that can introduce an alkyl/aryl sulfinyl unit into a substrate as a single substitution event. The S-functionalization reaction can be directed though interactions of the sulfenate oxygen and its counterion. Using computational methods, we demonstrate the factors that direct the stereoselective S-alkylation of a protected cysteinesulfenate. In another study, our methods predict that a nearby boronic ester can direct and accelerate an S-benzylation reaction by preforming a Lewis complex between the sulfenate oxygen and the boron atom. An unexpected off-shoot of this study suggests an H-bonding interaction during the alkylation of a sulfenate may facilitate the substitution reaction. [ABSTRACT FROM AUTHOR]

The activation of C-H bonds is a potent tool for modifying molecular structures in chemistry. This article details the steps involved in a novel ligand bearing a bicyclic [3.3.1]-nonane framework and bissulfoxide moiety. A palladium catalyzed allylic C-H oxidation method enables a direct benzyl-allylic functionalization with the bissulfoxide ligand. Bissulfoixde ligand possesses a rapidly constructed bicyclic [3.3.1] framework and it proved to be effective for enabling both N- and C-alkylation. A total of 13 C-H activation productions were reported with good to excellent yields. This report validated that it is necessary to include bissulfoxide as a ligand for superior reactivities. Naftifine was produced utilizing developed C-H functionalization methodology in good overall yields. [ABSTRACT FROM AUTHOR]

The numerous uses for plastics in various industries have led to an increase in its manufacturing on a global scale over time. The accumulation of plastic waste is a direct result of the daily rise in plastic demand. One of the effective and trending ways of reducing the impact of plastic waste on the environment is to pyrolyze it and use the oil obtained from it as fuel for power generation, heating, extraction of chemicals, or as an asphalt binder modifier. In this study, an attempt was made for the modification of asphalt binder with the oil obtained from plastic waste pyrolysis known as pyro-oil, and to analyse aging properties of the modified binder. This paper deals with the modification of VG30 binder with pyro-oil obtained from High Density Polyethylene (HDPE) plastic waste and the analysing the effect of aging on the modified binders. Pyro-oil is yielded from the pyrolysis process of HDPE at about 750°C. The modified binders were prepared by adding 1%, 2%, and 3% pyro-oil by total weight of VG30. The effect of aging for the unmodified and modified binders was analyzed using fourier transform infrared (FTIR) spectroscopy. The binders were short term aged and the changes in their chemical functionalities before and after aging were analyzed. Results of the FTIR test were used to calculate functional group indices for evaluating the aging characteristics of the modified binders. It was observed that binder chemistry is influenced by aging.

Katalysatorkontrolle über Stereogenität höherer Ordnung vergrößert den zugänglichen stereochemischen Raum erheblich, aber Methoden zur stereoselektiven Synthese dreifach stereogener Einheiten wurden bisher nicht beschrieben. In diesem Artikel berichten wir über die stereokontrollierte Synthese von dreifach stereogenen Triptycylsulfonen, deren Atropisomerie aus einer C(sp3)−S‐Bindung resultiert. Die katalysatorkontrollierte Oxidation eines stereodynamischen Thioethers in Gegenwart einer chiralen Phosphorsäure erlaubte dabei den selektiven Zugang zu enantiomerenangereicherten Triptycylsulfoxiden. Deren anschließende enantiospezifische und diastereoselektive katalytische Oxidation zu einem dreifach stereogenen Sulfon ermöglichte es so, die stereogene C−S‐Achse zu kontrollieren. Alle drei Stereoisomere wurden mit Enantio‐ und Diastereodivergenz und einer Stereoselektivität von bis zu (−sc) : (+sc) : (ap)=94 : 6 : <1 erhalten. [ABSTRACT FROM AUTHOR]

With the development of antimicrobial agents, researchers have developed new strategies through key regulatory systems to block the expression of virulence genes without affecting bacterial growth. This strategy can minimize the selective pressure that leads to the emergence of resistance. Quorum sensing (QS) is an intercellular communication system that plays a key role in the regulation of bacterial virulence and biofilm formation. Studies have revealed that the QS system controls 4–6% of the total number of P. aeruginosa genes, and quorum sensing inhibitors (QSIs) could be a promising target for developing new prevention and treatment strategies against P. aeruginosa infection. In this study, four series of phenyloxadiazole and phenyltetrazole sulfoxide derivatives were synthesized and evaluated for their inhibitory effects on P. aeruginosa PAO1 biofilm formation. Our results showed that 5b had biofilm inhibitory activity and reduced the production of QS-regulated virulence factors in P. aeruginosa. In addition, silico molecular docking studies have shown that 5b binds to the P. aeruginosa QS receptor protein LasR through hydrogen bond interaction. Preliminary structure–activity relationship and docking studies show that 5b has broad application prospects as an anti-biofilm compound, and further research will be carried out in the future to solve the problem of microbial resistance. [ABSTRACT FROM AUTHOR]

Sulfoxides and selenoxides oxidize thiols to disulfides while being reduced back to sulfides and selenides. While the reduction mechanism of sulfoxides to sulfides has been thoroughly explored experimentally as well as computationally, less attention has been devoted to the heavier selenoxides. In this work, we explore the reductive mechanism of dimethyl selenoxide, as an archetypal selenoxide and, for the sake of comparison, the reductive mechanism of dimethyl sulfoxide to gain insight into the role of the chalcogen on the reaction substrate. Particular attention is devoted to the key role of sulfurane and selenurane intermediates. Moreover, the capacity of these system to oxidize selenols rather than thiols, leading to the formation of selenyl sulfide bridges, is explored in silico. Notably, this analysis provides molecular insight into the role of selenocysteine in methionine sulfoxide reductase selenoenzyme. The activation strain model of chemical reactivity is employed in the studied reactions as an intuitive tool to bridge the computationally predicted effect of the chalcogen on the chalcogenoxide as well as on the chalcogenol. [ABSTRACT FROM AUTHOR]

The synthesis methods of sulfoxide compounds in recent years were reviewed in terms of whether they were in line with the concept of green chemistry, whether the selectivity and conversion rate were efficient, and whether the synthesis methods were novel. Among them, the most common synthesis method is sulfide oxidation, and after oxidation of oxide system, only sulfoxide is generated, and the yield is guaranteed; Friedel-Crafts sulfinylation reaction realizes the high-selectivity synthesis of pyrrole and sulfonamide for the first time. Visible light-catalyzed synthesis of sulfoxide only requires air as an oxidant, and the reaction conditions are simple and environmentally friendly, which is worthy of vigorous promotion. Since sulfoxide can form complexes with sulfur dioxide and nitrogen oxides in flue gas, sulfoxide is widely used in the field of flue gas desulfurization and denitrification. The rate can reach more than 90%. The system of sulfoxide, diol and diamine is mainly discussed, which has the best absorption effect and is of great significance for industrial production. [ABSTRACT FROM AUTHOR]

The aerobic photooxidation of sulfides into sulfoxides in eco-friendly solvents, notably water, at room temperature, represents a significant interest in the domain of synthetic chemistry. This study introduces four highly stable hexadentate Ir(III) complexes: [Ir(fpqen)](PF6) (1), [Ir(btqen)](PF6) (2), [Ir(bmpqen)](PF6) (3), and [Ir(bnqen](PF6) (4) (where bfpqen is N,N′-bis(2-(4-fluorophenyl)quinolin-8-yl)ethane-1,2-diamine, btqen is N,N′-bis(2-(4-tolyl)quinolin-8-yl)ethane-1,2-diamine, bmpqen is N,N′-bis(2-(4-methoxyphenyl)quinolin-8-yl)ethane-1,2-diamine, and bnqen is N,N′-bis(2-naphthylquinolin-8-yl)ethane-1,2-diamine). These complexes were synthesized utilizing an in situ inter-ligand C-N cross-coupling photoreaction of the precursors [Ir(L)2(en)](PF6) (L is 2-(4-fluorophenyl)quinoline, (2-(4-tolyl)quinoline, 2-(4-methoxyphenyl)quinoline or 2-naphthylquinoline, and en is 1,2-diamine) under benign conditions. This methodology furnishes a valuable and complementary approach for the in situ generation of multidentate complexes through a post-coordination inter-ligand-coupling strategy under mild conditions. Moreover, these hexadentate Ir(III) complexes exhibit pronounced catalytic activity and chemo-selectivity toward the aerobic photooxidations of sulfides into sulfoxides in aqueous media at room temperature, offering a new avenue for the sustainable synthesis of sulfoxides.

Diaryliodonium salts are useful arylating reagents that have been exploited widely. In this Communication, we demonstrate that heating diphenyliodonium triflate in the solvent DMSO leads to an unexpected arylation reaction. It is postulated that arylation of DMSO at oxygen, followed by a thia-Sommelet–Hauser rearrangement, leads to the formation of 2-thiomethylphenols. More substituted diaryliodonium salts and cyclic diaryliodonium salts are shown to be more stable and less likely to react with DMSO. In conclusion, when using iodonium salts dissolved in DMSO, beware of side-reactions.

In this article, we show that tribromide heterogenized on the surface of silica-coated magnetic nanoparticles modified with N2,N4,N6-tris(aminomethyl)-1,3,5-triazine-2,4,6-triamine [Fe3O4@SiO2-tris(triazine-triamine)-Br3] is a novel and efficient reusable nanocatalyst for the oxidation of sulfides to sulfoxides and oxidative coupling of thiols to disulfides using hydrogen peroxide as green oxidant. The structure of the as-fabricated Fe3O4@SiO2-tris(triazine-triamine)-Br3 was characterized by a series of spectroscopic techniques including FT-IR spectroscopy, SEM, TEM, EDX, VSM, XRD and TGA techniques. TEM and SEM analysis confirmed that the typical silica shell thickness was assessed to be around 20 nm. Recycling studies revealed that the Fe3O4@SiO2-tris(triazine-triamine)-Br3 could be easily recovered by a simple magnetic separation and recycled at least 6 times without deterioration in catalytic activity. [ABSTRACT FROM AUTHOR]

An efficient method for the direct methanethiolation of uracil and its derivatives was explored. Commercially available dimethyl sulfoxide was used as the methylthio source. A group of substituted uracils were successfully obtained in moderate to excellent yields when the combination of dimethyl sulfoxide and phenylphosphonic dichloride was used. [ABSTRACT FROM AUTHOR]