34896-80-5Relevant articles and documents
Flow Electrosynthesis of Sulfoxides, Sulfones, and Sulfoximines without Supporting Electrolytes
Amri, Nasser,Wirth, Thomas
, p. 15961 - 15972 (2021/07/20)
An efficient electrochemical flow process for the selective oxidation of sulfides to sulfoxides and sulfones and of sulfoxides toN-cyanosulfoximines has been developed. In total, 69 examples of sulfoxides, sulfones, andN-cyanosulfoximines have been synthesized in good to excellent yields and with high current efficiencies. The synthesis was assisted and facilitated through a supporting electrolyte-free, fully automated electrochemical protocol that highlights the advantages of flow electrolysis.
A μ-AsO4-Bridging Hexadecanuclear Ni-Substituted Polyoxotungstate
Lian, Chen,Li, Hai-Lou,Yang, Guo-Yu
, p. 3996 - 4003 (2021/04/07)
A novel tetrahedral μ-AsO4-bridging hexadecanuclear Ni-substituted silicotungstate (ST) Na21H10[(AsO4){Ni8(OH)6(H2O)2(CO3)2(A-α-SiW9O34)2}2]·60H2O (1) was made by the reactions of trivacant [A-α-SiW9O34]10- ({SiW9}) units with Ni2+ cations and Na3AsO4·12H2O and characterized by IR spectrometry, elemental analysis, thermogravimetric analysis (TGA), and powder X-ray diffraction (PXRD). 1 contains a novel polyoxoanion [(AsO4){Ni8(OH)6(H2O)2(CO3)2(A-α-SiW9O34)2}2]31- built by four trivacant Keggin [A-α-SiW9O34]10- fragments linked through an unprecedented [(AsO4){Ni8(OH)6(H2O)2(CO3)2}2]9+ cluster, where the tetrahedral AsO4 acts as an exclusively μ2-bridging unit to link multiple Ni centers; such a connection mode appears for the first time in polyoxometalate chemistry. Furthermore, the electrochemical and catalytic oxidation properties of compound 1 have been investigated.
A {Ti6W4}-Cluster-Substituted Polyoxotungstate: Synthesis, Structure, and Catalytic Oxidation Properties
Li, Hai-Lou,Lian, Chen,Yang, Guo-Yu
supporting information, p. 14622 - 14628 (2021/10/01)
A novel Ti-W-O-cluster-substituted tungstoantimonate (TA), [H2N(CH3)2]3Na4H9[{Ti6W4O18(OH)(H2O)3}(B-α-SbW9O33)3]·20H2O (1), has been made by hydrothermal reactions of trivacant [B-α-SbW9O33]9- units, Ti4+ cations, and WO42- anions in the presence of [H2N(CH3)2]·Cl and structurally characterized. Intriguingly, the polyoxoanion of 1 is constructed from three [B-α-SbW9O33]9- units and a previously unobserved decanuclear heterometallic Ti-W-O cluster [Ti6W4O18(OH)(H2O)3]11+ ({Ti6W4}) that is comprised of an octahedral [Ti6WO6(H2O)3]18+ cluster and an edge-sharing [W3O12(OH)]7- fragment via six W-O-Ti/W linkers. Furthermore, studies on the catalytic oxidation properties reveal that 1 possesses good catalytic activity toward the oxidation reactions of various sulfides and cyclooctene based on the environmentally friendly oxidant H2O2.
{Ti6}/{Ti10} Wheel Cluster Substituted Silicotungstate Aggregates
Li, Hai-Lou,Lian, Chen,Yang, Guo-Yu
, p. 16852 - 16859 (2021/11/13)
Two novel Ti-oxo wheel cluster substituted silicotungstates (STs) [H2N(CH3)2]9H9[Ti6O6(SiW10O37)3]·11H2O (1) and [H2N(CH3)2]16H10[Ti10O11(SiW10O37)2(SiW9O35)2]·14H2O (2) have been made by hydrothermal reactions. The polyoxoanion of 1 is a ring-shaped trimer where a Ti6O6 ({Ti6}) wheel cluster is encapsulated by three divacant [SiW10O37]10- (SiW10O37) fragments. However, 2 is built by two divacant SiW10O37 units and two rare trivacant [SiW9O35]12- (SiW9O35) fragments and further installs an unprecedented Ti10O11 ({Ti10}) double-wheel cluster. To the best of our knowledge, 2 is rare in POM chemistry. Studies on the catalytic oxidation properties reveal that 1 exhibits high catalytic activity toward the oxidation of various sulfides using H2O2 as an oxidant. Furthermore, 1 can be facilely recycled and reused for at least five cycles without obvious loss of catalytic activity.
General sulfone construction: Via sulfur dioxide surrogate control
Chen, Shihao,Li, Yaping,Wang, Ming,Jiang, Xuefeng
supporting information, p. 322 - 326 (2020/02/13)
A highly efficient one-step synthesis of alkyl-alkyl and aryl-alkyl sulfones with a facile combination of halides, sulfur dioxide surrogates and phosphate esters is described. When thiourea dioxide was employed as a reductive sulfur dioxide surrogate, alkyl-alkyl sulfones were obtained under transition metal free conditions. Aryl-alkyl sulfones were obtained with an extremely low catalytic loading (0.2 mol%) via altering the mask of sulfur dioxide surrogates to sodium dithionite. A phosphate ester was employed as a stable and readily available alkyl source. Notably, this protocol has been applied to the late-stage modification of natural products and bioactive molecules.
Three Zr(IV)-Substituted Polyoxotungstate Aggregates: Structural Transformation from Tungstoantimonate to Tungstophosphate Induced by pH
Li, Hai-Lou,Lian, Chen,Yang, Guo-Yu,Yin, Da-Peng
, p. 12842 - 12849 (2020/09/15)
Three novel Zr-substituted polyoxotungstate aggregates [H2N(CH3)2]7NaH2[Zr2Sb2O3(A-α-PW9O34)2]·16H2O (1), [H2N(CH3)2]6H12[ZrSb4(OH)O2(A-α-PW8O32)(A-α-PW9O34)]2·33H2O (2), and [H2N(CH3)2]4Na11.5H4.5[Zr4W8Sb4P5O49(OH)5(B-α-SbW9O33)2]·53H2O (3) have been made in hydrothermal reactions of the [B-α-SbW9O33]9- precursor with Zr4+ cations and PO43- anions in the presence of dimethylamine hydrochloride and sodium acetate buffer (pH = 4.8) and structurally characterized. Different pH values induce structural transformation from tungstoantimonate (TA) to tungstophosphate (TP). 1 is a di-Zr-substituted sandwich-type TP, the tetranuclear heterometallic [Zr2Sb2O3]8+ entity sandwiched by two [A-α-PW9O34]9- moieties. 2 is a double sandwich-type structure, which can be perceived as two equivalent sandwiched [Sb3(PW8O32)(PW9O34)]11- further sandwiching one [Sb2Zr2(OH)2O4]4+ core to form a novel large-size sandwich-type architecture. Different from 1 and 2, 3 is a tetra-Zr-substituted sandwiched configuration, in which two [B-α-SbW9O33]9- fragments sandwich a unique 21-core Sb-P-W-Zr oxo cluster ({Zr4W8Sb4P5}). Furthermore, the catalytic oxidation of aromatic thioethers by 3 as the heterogeneous catalyst has been investigated, showing high conversion and remarkable selectivity as well as excellent recyclability.
Two Ce3+-Substituted Selenotungstates Regulated by N, N-Dimethylethanolamine and Dimethylamine Hydrochloride
Li, Hai-Lou,Lian, Chen,Chen, Li-Juan,Zhao, Jun-Wei,Yang, Guo-Yu
, p. 8442 - 8450 (2019/07/04)
Two multi-Ce3+-substituted selenotungstates (STs), [HDMEA][H2N(CH3)2]4H3Na4[Ce2(H2O)6(DMEA)W4O9(α-SeW9O33)3]·26H2O (1) and [H2N(CH3)2]10H4Na10[Ce2W4O9(H2O)7(α-SeW9O33)3]2·63H2O (2), were prepared by the one-pot approach of sodium tungstate, sodium selenite, and lanthanide nitrate in an acidic water solution in the presence of N,N-dimethylethanolamine (DMEA) or dimethylamine hydrochloride (DMAHC). 1 was obained in the presence of DMEA, whereas 2 was synthesized in the presence of DMAHC. The trimeric polyoxoanion of 1 contains an unusual V-shaped [Se3W29O103]20- group embracing a prominent heterometal oxide fragment, [Ce2(H2O)6(DMEA)W2O5]8+, and the hexameric polyoxoanion of 2 is constructed from two equivalent trimeric [Ce2W4O9(H2O)7(SeW9O33)3]2 24- subunits through two -O-W-O-Ce-O- linkages. The most worthy of attention is that the polyoxoanion of 1 can be approximatively viewed as a half of the polyoxoanion of 2 because of the coordination and blocking effect of DMEA. The stability of 1 and 2 in different water pH values was studied by electrospray ionization mass spectroscopy (ESI-MS), and the results manifest that 1 and 2 are stable in pH = 3.5-7.5 and 3.5-7.0, respectively. The oxidation reactions of aromatic sulfides catalyzed by H2O2 were studied when 1 or 2 worked as a catalyst, and experimental results reveal that 1 or 2 can serve as available catalysts for the oxidation of aromatic sulfides under mild conditions.
A Class of Amide Ligands Enable Cu-Catalyzed Coupling of (Hetero)aryl Halides with Sulfinic Acid Salts under Mild Conditions
Zhao, Jinlong,Niu, Songtao,Jiang, Xi,Jiang, Yongwen,Zhang, Xiaojing,Sun, Tiemin,Ma, Dawei
, p. 6589 - 6599 (2018/05/31)
The amide derived from 4-hydroxy-l-proline and 2,6-dimethylaniline is a powerful ligand for Cu-catalyzed coupling of (hetero)aryl halides with sulfinic acid salts, allowing the formation of a wide range of (hetero)aryl sulfones from the corresponding (hetero)aryl halides at considerably low catalytic loadings. The coupling of (hetero)aryl iodides and sodium methanesulfinate proceeds at room temperature with only 0.5 mol % CuI and ligand, representing the first example for Cu-catalyzed arylation at both low catalytic loading and room temperature.
Synthesis and biological properties of aryl methyl sulfones
Navarro, Lorena,Rosell, Gloria,Sánchez, Silvia,Boixareu, Núria,Pors, Klaus,Pouplana, Ramon,Campanera, Josep M.,Pujol, M. Dolors
, p. 4113 - 4126 (2018/07/06)
A novel group of aryl methyl sulfones based on nonsteroidal anti-inflammatory compounds exhibiting a methyl sulfone instead of the acetic or propionic acid group was designed, synthesized and evaluated in vitro for inhibition against the human cyclooxygenase of COX-1 and COX-2 isoenzymes and in vivo for anti-inflammatory activity using the carrageenan induced rat paw edema model in rats. Also, in vitro chemosensitivity and in vivo analgesic and intestinal side effects were determined for defining the therapeutic and safety profile. Molecular modeling assisted the design of compounds and the interpretation of the experimental results. Biological assay results showed that methyl sulfone compounds 2 and 7 were the most potent COX inhibitors of this series and best than the corresponding carboxylic acids (methyl sulfone 2: IC50 COX-1 = 0.04 and COX-2 = 0.10 μM, and naproxen: IC50 COX-1 = 11.3 and COX-2 = 3.36 μM). Interestingly, the inhibitory activity of compound 2 represents a significant improvement compared to that of the parent carboxylic compound, naproxen. Further support to the results were gained by the docking studies which suggested the ability of compound 2 and 7 to bind into COX enzyme with low binding free energies. The improvement of the activity of some sulfones compared to the carboxylic analogues would be performed through a change of the binding mode or mechanism compared to the standard binding mode displayed by ibuprofen, as disclosed by molecular modeling studies. So, this study paves the way for further attention in investigating the participation of these new compounds in the pain inhibitory mechanisms. The most promising compounds 2 and 7 possess a therapeutical profile that enables their chemical scaffolds to be utilized for development of new NSAIDs.
Bovine serum albumin-cobalt(II) Schiff base complex hybrid: An efficient artificial metalloenzyme for enantioselective sulfoxidation using hydrogen peroxide
Tang, Jie,Huang, Fuping,Wei, Yi,Bian, Hedong,Zhang, Wei,Liang, Hong
, p. 8061 - 8072 (2016/06/06)
An artificial metalloenzyme (BSA-CoL) based on the incorporation of a cobalt(ii) Schiff base complex {CoL, H2L = 2,2′-[(1,2-ethanediyl)bis(nitrilopropylidyne)]bisphenol} with bovine serum albumin (BSA) has been synthesized and characterized. Attention is focused on the catalytic activity of this artificial metalloenzyme for enantioselective oxidation of a variety of sulfides with H2O2. The influences of parameters such as pH, temperature, and the concentration of catalyst and oxidant on thioanisole as a model are investigated. Under optimum conditions, BSA-CoL as a hybrid biocatalyst is efficient for the enantioselective oxidation of a series of sulfides, producing the corresponding sulfoxides with excellent conversion (up to 100%), chemoselectivity (up to 100%) and good enantiomeric purity (up to 87% ee) in certain cases.
