cas 7321-58-6, 2-Bromophenylmethylsulfoxide

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Chiral Ligands in Hypervalent Iodine Compounds: Synthesis and Structures of Binaphthyl-Based λ3-Iodanes
Several novel binaphthyl-based chiral hypervalent iodine(III) reagents have been prepared and structurally analysed. Various asymmetric oxidative reactions were applied to evaluate the reactivities and stereoselectivities of those reagents. Moderate to excellent yields were observed; however, very low stereoselectivities were obtained. NMR experiments indicated that these reagents are very easily hydrolysed in either chloroform or DMSO solvents leading to the limited stereoselectivities. It is concluded that the use of chiral ligands is an unsuccessful way to prepare efficient stereoselective iodine(III) reagents.
Zhang, Huaiyuan,Cormanich, Rodrigo A.,Wirth, Thomas
supporting information

(2021/12/22)

A Bimetallic Ag/Ti-Based Coordination Polymer as a Catalyst for Electrocatalytic CO2 Reduction and Selective Sulfide Oxidation
The first example of heterometallic Ag/Ti bimetallic-based coordination polymer was synthesized using salicylic acid as the ligand. The uniform Ag/Ti?O rod array has efficient electrocatalytic CO2 reduction activity with a Faradaic efficiency (FE) of 90.3 % at ?0.88 V (vs RHE) and a maximum TOF of 658 h?1 at ?1.08 V. The chemical catalytic property of the Ag/Ti?O rod was also studied, and the results showed that the Ag/Ti?O rod has good catalytic performance for selective oxidation of sulfide to sulfoxide.
Li, Lei-Jiao,Liu, Chao,Liu, Weisheng,Pan, Fuxing,Ru Liu, Xue,Wu, Yi-Xin,Yu, Wei-Dong
(2022/03/08)

Two enantiocomplementary Baeyer-Villiger monooxygenases newly identified for asymmetric oxyfunctionalization of thioether
Two enantiocomplementary Baeyer-Villiger monooxygenases RaBVMO and AmBVMO were identified by genome mining for the asymmetric sulfoxidation. Both recombinant BVMOs have optimal pH of 9.0 and temperature of 35 °C. The half-lives of RaBVMO and AmBVMO at 30 °C were 24.4 and 24.6 h. RaBVMO and AmBVMO exhibited broad substrate spectrum and could catalyze the oxidization of various compounds including fatty ketones, cyclic ketones, and thioethers. Kinetic parameters analysis revealed that both RaBVMO and AmBVMO displayed higher catalytic efficiency toward thioanisole than cyclohexanone. As much as 50 mM thioanisole could be completely oxidized by AmBVMO and RaBVMO with 99% (R) and 95% (S), respectively. Molecular docking analysis further provides evidence for the complementary enantioselectivity of RaBVMO and AmBVMO. Our results demonstrate the potential application of the two novel BVMOs in asymmetric synthesis of sulfoxides.
Liu, Yafei,Ni, Ye,Wei, Shiyu,Xu, Guochao,Zhou, Jieyu
(2021/08/19)

Synthesis method of sulfoxide compound
The invention discloses a method for preparing sulfoxide derivatives with industrial application value through substituted diaryl (heterocyclic aryl) and aryl (heterocyclic aryl) alkyl sulfide compounds. Under electrochemical reaction conditions, diaryl (heterocyclic aryl) and aryl (heterocyclic aryl) alkyl sulfide compounds which are wide in source and easy to prepare and have structural diversity are used as raw materials, lithium perchlorate (LiClO4) is used as an electrolyte, acetonitrile (CH3CN) is used as a solvent, and oxygen is used as an oxidizing agent to prepare the diaryl (heterocyclic aryl) and aryl (heterocyclic aryl) alkyl sulfoxide derivatives. Compared with reported preparation methods of sulfoxide derivatives, the preparation method disclosed by the invention is green, environment-friendly, safe, energy-saving, wide in substrate application range, good in compatibility of product functional groups, easy in obtaining of raw materials and simple and convenient to operate.
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Paragraph 0031-0033; 0077-0079

(2021/04/07)

Catalyst-free visible light-mediated selective oxidation of sulfides into sulfoxides under clean conditions
A facile and efficient visible-light-mediated method for directly converting sulfides into sulfoxides under clean conditions without using any photocatalysts is reported. This method exhibited favourable compatibility with functional groups and afforded a series of sulfoxides with high selectivity and yields. Moreover, in order to shed more light on such a transformation, detailed mechanism studies were carried out both experimentally and theoretically. The readily accessible, low-cost and eco-friendly nature of the developed method will endow it with attractive applications in chemical synthesis.
Fan, Qiangwen,Zhu, Longwei,Li, Xuhuai,Ren, Huijun,Wu, Guorong,Zhu, Haibo,Sun, Wuji
supporting information
p. 7945 - 7949
(2021/11/01)

Covalent Organic Frameworks toward Diverse Photocatalytic Aerobic Oxidations
Photoactive two-dimensional covalent organic frameworks (2D-COFs) have become promising heterogenous photocatalysts in visible-light-driven organic transformations. Herein, a visible-light-driven selective aerobic oxidation of various small organic molecules by using 2D-COFs as the photocatalyst was developed. In this protocol, due to the remarkable photocatalytic capability of hydrazone-based 2D-COF-1 on molecular oxygen activation, a wide range of amides, quinolones, heterocyclic compounds, and sulfoxides were obtained with high efficiency and excellent functional group tolerance under very mild reaction conditions. Furthermore, benefiting from the inherent advantage of heterogenous photocatalysis, prominent sustainability and easy photocatalyst recyclability, a drug molecule (modafinil) and an oxidized mustard gas simulant (2-chloroethyl ethyl sulfoxide) were selectively and easily obtained in scale-up reactions. Mechanistic investigations were conducted using radical quenching experiments and in situ ESR spectroscopy, all corroborating the proposed role of 2D-COF-1 in photocatalytic cycle.
Liu, Shuyang,Tian, Miao,Bu, Xiubin,Tian, Hua,Yang, Xiaobo
supporting information
p. 7738 - 7744
(2021/05/07)

Synergistic cooperative effect of CF3SO2Na and bis(2-butoxyethyl)ether towards selective oxygenation of sulfides with molecular oxygen under visible-light irradiation
A safe, practical and eco-friendly method for the switchable synthesis of sulfoxides and sulfones through visible-light-initiated oxygenation of sulfides at ambient temperature under transition-metal-, additives-free and minimal solvent conditions. The synergistic catalytic efforts between CF3SO2Na and 2-butoxyethyl ether represents the key promoting factor for the reaction. This journal is
Liu, Kai-Jian,Wang, Zheng,Lu, Ling-Hui,Chen, Jin-Yang,Zeng, Fei,Lin, Ying-Wu,Cao, Zhong,Yu, Xianyong,He, Wei-Min
supporting information
p. 496 - 500
(2021/01/28)

Electrochemical oxygenation of sulfides with molecular oxygen or water: Switchable preparation of sulfoxides and sulfones
A practical and eco-friendly method for the controllable aerobic oxygenation of sulfides by electrochemical catalysis was developed. The switchable preparation of sulfoxides and sulfones was effectively controlled by reaction time, in which both molecular oxygen and water can be used as the oxygen source under catalyst and external oxidant-free conditions. The electrochemical protocol features a broad substrate scope and excellent site selectivity and is successfully applied to the modification of some sulfide-containing pharmaceuticals and their derivatives. This journal is
Li, Jin-Heng,Li, Yang,Sun, Qing,Xue, Qi,Zhang, Ting-Ting
supporting information
p. 10314 - 10318
(2021/12/17)

Electrochemical Scalable Sulfoxidation of Sulfides with Molecular Oxygen and Water
An efficient and chemoselective synthesis of sulfoxides through the electrooxidation of sulfides has been well developed. This protocol takes advantage of electricity as the terminal oxidant and of molecular oxygen and water as the oxygen atom sources. A variety of structurally diverse sulfoxide compounds are assembled in moderate to excellent yields. The scaled-up reactions at 6–20 mmol show the good practicability and application potential of this methodology. A possible free radical mechanism has been proposed to rationalize the reaction procedure.
Cheng, Zhen,Gao, Xinglian,Yao, Lingling,Wei, Zhaoxin,Qin, Guohui,Zhang, Yonghong,Wang, Bin,Xia, Yu,Abdukader, Ablimit,Xue, Fei,Jin, Weiwei,Liu, Chenjiang
p. 3743 - 3747
(2021/07/26)

Method for preparing sulfoxide compound by catalyzing thioether compound to be oxidized by visible light excitation aqueous solution quantum dots
The invention provides a method for preparing a sulfoxide compound through oxidation of a visible light excitation aqueous solution quantum dot catalytic thioether compound. Belong to photocatalysis synthesis technical field. To the method, an aqueous sol
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Paragraph 0031

(2021/11/14)

Flow Electrosynthesis of Sulfoxides, Sulfones, and Sulfoximines without Supporting Electrolytes
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.
Amri, Nasser,Wirth, Thomas
p. 15961 - 15972
(2021/07/20)

Accelerated Oxidation of Organic Sulfides by Microdroplet Chemistry
We report the rapid oxidation of organic sulfides to sulfoxides by means of microdroplet chemistry at room temperature using a spray solution containing an organic sulfide dissolved in water/methanol, dilute (11%-14%) sodium hypochlorite (NaClO), and 5% chloroauric acid (HAuCl4). Ultrasonic nebulization, easy ambient sonic-spray ionization, or electrosonic spray ionization serves as the microdroplet source. High-resolution mass spectrometry was used as an online detector, and nuclear magnetic resonance was used as an offline detector. We found that the sulfoxide yields vary between 66 and 95%, the highest rate of product formation is 195 mg/min for benzyl phenyl sulfoxide, and the time required is a few minutes, which is much less than that required for the conventional means of achieving this chemical transformation. We also applied this microdroplet method to protein fingerprinting. We found that protein sequences containing methionine can be quickly oxidized, providing useful information for protein structure determinations.
Li, Jia,Liu, Chengyuan,Chen, Hao,Zare, Richard N.
p. 5011 - 5015
(2021/04/02)

Modulation of photochemical oxidation of thioethers to sulfoxides or sulfones using an aromatic ketone as the photocatalyst
We have developed an eco-friendly and chemo-selective photocatalytic synthesis of sulfoxides or sulfones via oxidation of sulfides (thioethers) at ambient temperature using air or O2 as the oxidant. An inexpensive thioxanthone was used as the photocatalyst. Our method offers excellent chemical yields and good functional group tolerance. The hydrogen bonding between hexafluoro-2-propanol (HFIP) and sulfoxides may play an important role in minimizing the over-oxidization of sulfoxides.
Zhao, Bin,Hammond, Gerald B.,Xu, Bo
supporting information

(2021/09/13)

Lanthanide complexes of anthraquinone-1,8-disulfonate: Syntheses, structures and catalytic studies
Two isostructural series of four lanthanide coordination complexes have been synthesized by hydrothermal method with anthraquinone-1,8-disulfonate as the anionic ligand. The complexes also comprise K+ ions that participate into coordination to
Cao, Fu-Yu,Chen, Xu-Dong,Gao, Hui-Lei,Han, Jie,Huang, Meng-Ping,Zhao, Xiao-Li
(2021/06/07)

Lanthanide complexes based on an anthraquinone derivative ligand and applications as photocatalysts for visible-light driving photooxidation reactions
Four isostructural lanthanide coordination complexes based on 3,7-diamino-9,10-anthraquinone-2,6-disulfonate (dianionic, L) have been synthesized by hydrothermal method, namely [Er(L)(H2O)6]?[Er(H2O)8]?2L?8H2O (Er-L), [Tm(L)(H2O)6]?[Tm(H2O)8]?2L?8.5H2O (Tm-L), [Yb(L)(H2O)6]?[Yb(H2O)8]?2L?9H2O (Yb-L), [Lu(L)(H2O)6]?[Lu(H2O)8]?2L?9H2O (Lu-L). Single-crystal X-ray analysis reveals the existence of both coordinated and free ligand L in the crystal structure. Versatile sulfonate groups on these distinct L ligands, together with very rich coordinated and lattice water molecules, form a lot of hydrogen-bonding motifs that contribute to the stabilization of the crystal packing. It is interesting that the ligands stack into columns through strong π-π interactions and the centroid-centroid distances are between 3.281 and 3.331 ?. These ligands are stacked in an alternate off-set mode to avoid the steric hindrance between the bulky sulfonate groups, generating a repeated structural unit involving six stacked ligands. These lanthanide complexes proved to be good heterogeneous photocatalyst for promoting the visible-light driving photooxidation reactions of diarylacetylenes and thioethers. The Er-L complex exhibited the best catalytic activity and showed good catalytic efficiency over a wide range of substrates for both reaction systems. The Er-L photocatalyst can be easily isolated by simple filtration as crystalline material upon completion of the photooxidation reaction without structure change, and can be recycled for at least five catalytic cycles with persistent catalytic efficiency without any need of activation or regeneration. This family of lanthanide complexes represent a category of promising heterogeneous photocatalysts in terms of green chemistry, with the potential of promoting organic transformations highly efficiently under the irradiation of visible light.
Zhu, Ting-Ting,Tao, Yu-Tong,Sun, Yue,Wang, Xue,Zhang, Xiao-Wen,Chai, Jia-Lu,Han, Jie,Zhao, Xiao-Li,Chen, Xu-Dong
(2021/04/05)

Preparation of S-2-halophenyl-2,1-benzothiazines
Derivatives of 2,1-benzothiazines are useful synthetic intermediates for a variety of applications. We became interested in developing a one-pot procedure to S-2-halophenyl-2,1-benzothiazines as potential precursors to P,N type ligands for metals. Accordingly, we reacted S-2-halophenyl-S-methylsulfoximines with 2-bromobenzaldehydes using the Buchwald-Hartwig reaction under conditions previously developed in our laboratory. We found that 2-halophenylmethyl sulfoximines show lower reactivity in process than methylphenyl sulfoximine. Among the 2-(S)-2-halophenyl-(S)-methylsulfoximines tested, S-2-fluorophenyl-S-methyl sulfoximine afforded higher yields of benzothiazines than the bromine- or chlorine-substituted congeners. In the coupling of S-2-halophenyl-S-methylsulfoximines to 2-bromobenzaldehyde, using Ruphos as a ligand gave the best yields.
Garimalla, Aswin,Harmata, Michael
(2021/03/15)

{Cu8} Cluster-Sandwiched Polyoxotungstates and Their Polymers: Syntheses, Structures, and Properties
Four inorganic-organic hybrid octa-Cu cluster sandwiched polyoxotungstates (POTs), [Cu8(H2O)2(en)4(B-α-H2SiW9O34)2] (1), [Cu8(H2O)2(en)4(B-α-H2GeW9O34)2] (2), K2[Cu8(en)4(B-α-HSiW9O34)2]·6H2O (3), and K2[Cu8(en)4(B-α-HGeW9O34)2]·2H2O (4) (en = ethylenediamine), were hydrothermally made and characterized by single-crystal X-ray diffraction, infrared spectra, powder X-ray diffraction, and thermogravimetric analysis, respectively. Structure analysis reveals that the polyoxoanion of 1/2 is a discrete dimer built by two trivalent Keggin [B-α-XW9O34]10- (X = Si/Ge) fragments and one octa-Cu cluster, whereas 3 and 4 display a two-dimensional network built by octa-Cu-sandwiched POT units via substitution of coordinated water on polyanions of 1 and 2 and further expand into a three-dimensional framework via K cation bridges. Ultraviolet-visible diffuse reflectance spectra reveal that 1-4 are potential semiconductor materials. Moreover, its visible light-driven catalytic H2 evolution activity, electrochemical properties, catalysis for oxygenation reactions of thioethers, and magnetic behaviors have been investigated in detail.
Sun, Jun-Jun,Wang, Wei-Dong,Li, Xu-Yan,Yang, Bai-Feng,Yang, Guo-Yu
p. 10459 - 10467
(2021/07/21)

Visible-Light-Driven Oxidative Cleavage of Alkenes Using Water-Soluble CdSe Quantum Dots
The oxidative cleavage of C=C bonds is an important chemical reaction, which is a popular reaction in the photocatalytic field. However, high catalyst-loading and low turnover number (TON) are general shortcomings in reported visible-light-driven reactions. Herein, the direct oxidative cleavage of C=C bonds through water-soluble CdSe quantum dots (QDs) is described under visible-light irradiation at room temperature with high TON (up to 3.7×104). Under the same conditions, water-soluble CdSe QDs could also oxidize sulfides to sulfoxides with 51–84 % yields and TONs up to 3.4×104. The key features of this photocatalytic protocol include high TONs, wide substrates scope, low catalyst loadings, simple and mild reaction conditions, and molecular O2 as the oxidant.
Li, Jianing,Zhao, Jingnan,Ma, Cunfei,Yu, Zongyi,Zhu, Hongfei,Yun, Lei,Meng, Qingwei
p. 4985 - 4992
(2021/10/16)

Assembly of a Hexameric Cluster of Polyoxomolybdotriphosphonate Builts from [Zn(H2O){TeMo6O21}{N(CH2PO3)3}]6-Subunits and Its Optical and Catalytic Properties
The crown-shaped organotriphosphonate-modified 36-molybdenum cluster (NH4)18Na7H11[Zn(H2O)TeMo6O21{N(CH2PO3)3}]6·23H2O (1) has been synthesized, which is the largest zinc-containing organophosphonate-based polyoxometalate to date. Compound 1 was prepared in buffer solution (pH 5.5) with heptamolybdate and amino trimethylene phosphonic acid (ATMP) as the organic ligand. The polyanion constructed from a hexmeric assembly of [Zn(H2O){TeMo6O21}{N(CH2PO3)3}]6- subunits has been fully investigated by a few characterization methods. In this work, we discovered that 1 exhibited reversible photochromism and it changed from white to reddish brown upon UV irradiation. In addition, compound 1, as a catalyst, can oxidize sulfides to sulfoxides, showing a high yield/conversion and a good selectivity.
Kong, Hui,Li, Keli,Liu, Siyu,Ma, Pengtao,Niu, Jingyang,Wang, Jingping,Wang, Yaqiong,Xu, Qian
p. 15759 - 15767
(2021/10/20)

A μ-AsO4-Bridging Hexadecanuclear Ni-Substituted Polyoxotungstate
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.
Lian, Chen,Li, Hai-Lou,Yang, Guo-Yu
p. 3996 - 4003
(2021/04/07)

A {Ti6W4}-Cluster-Substituted Polyoxotungstate: Synthesis, Structure, and Catalytic Oxidation Properties
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.
Li, Hai-Lou,Lian, Chen,Yang, Guo-Yu
supporting information
p. 14622 - 14628
(2021/10/01)

{Ti6}/{Ti10} Wheel Cluster Substituted Silicotungstate Aggregates
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.
Li, Hai-Lou,Lian, Chen,Yang, Guo-Yu
p. 16852 - 16859
(2021/11/13)

Chiral: N, N ′-dioxide-iron(iii)-catalyzed asymmetric sulfoxidation with hydrogen peroxide
A highly enantioselective sulfoxidation of various sulfides has been achieved by a N,N′-dioxide-iron(iii) complex with 35% aq. H2O2 as the oxidant. The utility of the current method was demonstrated by asymmetric gram-scale synthesis of drug molecule (R)-modafinil. Moreover, a possible working mode was provided to elucidate the chiral induction.
Dong, Shunxi,Feng, Lili,Feng, Xiaoming,Liu, Xiaohua,Wang, Fang
supporting information
p. 3233 - 3236
(2020/03/23)

Alloxan-catalyzed biomimetic oxidations with hydrogen peroxide or molecular oxygen
Inspired by biological flavin catalysis, the nonionic alloxan derivatives were applied as the biomimetic catalysts for various oxidations, catalyzing oxidations of sulfides and amines with hydrogen peroxide or molecular oxygen under mild conditions with high yields in a short time. The whole catalytic cycle has been verified to be a biomimetic approach through the formation of the alloxan hydroperoxide reactive intermediate. Additionally, encouraging asymmetric catalytic results have been obtained with an easily prepared chiral alloxan in a sulfoxidation reaction.
Zhang, Shiqi,Li, Guangxun,Li, Ling,Deng, Xiongfei,Zhao, Gang,Cui, Xin,Tang, Zhuo
p. 245 - 252
(2019/12/24)

Method for preparing sulfoxide compounds through catalytic oxidation of thioether by nickel compound
The invention relates to a method for preparing sulfoxide compounds through catalytic oxidation of thioether by a nickel compound, wherein the method comprises the steps: mixing a solution containingthioether and an oxidant with a nickel catalyst, and carrying out a reaction to obtain the sulfoxide compounds. Compared with the prior art, the method has the advantages of high catalytic activity, stable properties, mild reaction conditions, high yield, good substrate universality and the like, and has great application potential in the aspect of drug intermediate synthesis.
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(2020/06/05)

Selective oxidation of (hetero)sulfides with molecular oxygen under clean conditions
The development of eco-friendly and switchable catalytic systems for the conversion of a sole raw-material into distinct high-value products is a particularly attractive concept and a daunting synthetic challenge. In the present work, the first example of efficient and selective oxidation of sulfides to sulfones and sulfoxides using molecular oxygen under clean conditions was established.
Liu, Kai-Jian,Deng, Ji-Hui,Yang, Jie,Gong, Shao-Feng,Lin, Ying-Wu,He, Jun-Yi,Cao, Zhong,He, Wei-Min
supporting information
p. 433 - 438
(2020/02/13)

Oxidation of aromatic sulfides with molecular oxygen: Controllable synthesis of sulfoxides or sulfones
The recent development of selective oxidation of aromatic sulfides with molecular oxygen was highlighted. The sulfoxides and sulfones could be obtained by simply switching the reaction media, i.e., bis(2-butoxyethyl)ether (BBE) or poly(ethylene glycol)dimethyl ether (PEGDME). The application of the high-boiling-point polyether as an initiator and green media can eliminate the need of large quantities of additives and volatile solvents. This strategy represents an economic and eco-friendly method that could find potential applications.
Tang, Lili,Du, Kejie,Yu, Bing,He, Liangnian
p. 2991 - 2992
(2020/03/24)

Emodinas a novel organic photocatalyst for selective oxidation of sulfides under mild conditions
Herein, we have developed naturally-occurringEmodin, which is commercially available at low-cost, as a novel organic photocatalyst for the first time.Emodinwas successfully employed in the selective oxidation of sulfides promoted by visible-light, deliver
Li, Min,Lou, Jiangli,Rao, Yijian,Yuan, Zhenbo,Zhang, Yan
p. 19747 - 19750
(2020/06/04)

A Lacunary Polyoxovanadate Precursor and Transition-Metal-Sandwiched Derivatives for Catalytic Oxidation of Sulfides
A SeO3-centered lacunary Keggin-type heteropolyoxovanadate (hetero-POV) K6H2[SeV10O28(SeO3)3]?14 H2O (1) was isolated by one-pot reaction of KVO3 and SeOsu
Wan, Rong,He, Peipei,Liu, Zhen,Ma, Xinyi,Ma, Pengtao,Singh, Vikram,Zhang, Chao,Niu, Jingyang,Wang, Jingping
p. 8760 - 8766
(2020/05/25)

Visible-Light-Responsive Anthraquinone Functionalized Covalent Organic Frameworks for Metal-Free Selective Oxidation of Sulfides: Effects of Morphology and Structure
Visible-light-responsive covalent organic frameworks (COFs) as photocatalysts for metal-free organic reactions are highly desirable due to their structural controllability and molecular functionality. In this study, we describe the fabrication of an anthr
An, Guangyu,Bai, Guoyi,Lan, Xingwang,Li, Qing,Ricardez-Sandoval, Luis,Wang, Zhenguang
p. 6664 - 6675
(2020/07/16)

Accurate Regulating of Visible-Light Absorption in Polyoxotitanate-Calix[8]arene Systems by Ligand Modification
With use of a macrocyclic polyphenol, tert-butylcalix[8]arene (TBC[8]), as ligands, a series of TBC[8]-stabilized {Ti4O2}clusters, containing penta- and hexacoordinated Ti centers, were synthesized. Such complexes are "core-shell" shaped containing a {Ti4O2} core arranged in a zigzag fashion. While outer walls of the clusters are decorated by deprotonated TBC[8], their upper and lower surfaces can be modified by various O- or N-donor ligands, and the ratio of the penta- and hexacoordinated Ti(IV) centers in the {Ti4O2} core can be precisely regulated from 4:0, to 3:1, to 2:2, to 1:3, and finally to 0:4. The combined coordination of different ligands in the axial direction shows significant influence on the adsorption of the TBC[8]-Ti4 system in the visible-light region, and their absorption edge can be precisely regulated from 600 to 700 nm. The above structural functionalization in the TBC[8]-Ti4 system also tunes their photocatalytic H2 production activities and oxidative desulfurization ability. Thus, for the first time, by confining the polyoxotitanium cluster in macrocyclic molecules, we provide an example of understanding the structure-property relationship of titanium-oxygen materials by ligand modification.
Liu, Chao,Yang, Xin-Xue,Yi, Xiao-Yi,Yu, Wei-Dong
(2020/06/08)

Three Zr(IV)-Substituted Polyoxotungstate Aggregates: Structural Transformation from Tungstoantimonate to Tungstophosphate Induced by pH
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.
Li, Hai-Lou,Lian, Chen,Yang, Guo-Yu,Yin, Da-Peng
p. 12842 - 12849
(2020/09/15)

Efficient Generation of Singlet Oxygen and Photooxidation of Sulfide into Sulfoxide via Tuning the Ancillary of Bicyclometalated Iridium(III) Complexes
With 2-phenylquinoline (pq) as a cyclometalated ligand, a series of cationic Ir(III) complexes [Ir(pq)2(L1)2](PF6) (L1 is pyridine (1a), 4-methoxypyridine (1b), 4-dimethylaminopyridine (1c), and 4-acetylpyridine (1d)) and
Li, Li-Ping,Ye, Bao-Hui
p. 7775 - 7784
(2019/06/17)

Electrochemical oxidations of thioethers: Modulation of oxidation potential using a hydrogen bonding network
A highly efficient chemo-selective electrochemical oxidation of thioethers to sulfoxides and sulfones was developed. The hydrogen bonding network generated from hexafluoro-2-propanol (HFIP) and acetic acid (AcOH) plays an important role in the modulation of oxidation potential. The hydrogen bonding network complexes strongly with the sulfoxide, making it less prone to further oxidation. Therefore, thioethers can be selectively electrochemically oxidized to sulfoxides and over-oxidization could be minimized. Moreover, this modulation of oxidization via hydrogen bonding was supported by density functional theory (DFT) calculations and cyclic voltammetry experiments.
Liu, Shiwen,Chen, Bocheng,Yang, Yi,Yang, Yuhao,Chen, Qianjin,Zeng, Xiaojun,Xu, Bo
(2019/11/28)

Synthesis and nano-Pd catalyzed chemoselective oxidation of symmetrical and unsymmetrical sulfides
A highly chemoselective, efficient and nano-Pd catalyzed protocol for the rapid construction of sulfoxides and sulfones via the oxidation of symmetrical and unsymmetrical sulfides using H2O2 as an oxidant has been developed, respectively. The ready availability of starting materials, easy recovery and reutilization of the catalyst, wide substrate scope, and high yields make this protocol an attractive alternative. The process also involves the metal-free and microwave-promoted synthesis of symmetrical diarylsulfides, and FeCl3-mediated preparation of symmetrical diaryldisulfides through the reaction of arenediazonium tetrafluoroborates with Na2S·9H2O as a sulfur source. In addition, unsymmetrical sulfides were generated via the K2CO3-mediated reaction of arenediazonium tetrafluoroborates with symmetrical disulfides.
Li, Xing,Du, Jia,Zhang, Yongli,Chang, Honghong,Gao, Wenchao,Wei, Wenlong
p. 3048 - 3055
(2019/03/21)

Switchable Synthesis of Aryl Sulfones and Sulfoxides through Solvent-Promoted Oxidation of Sulfides with O2/Air
A practical and switchable method for the synthesis of aryl sulfones and sulfoxides via sulfide oxidation was developed. The chemoselectivities of products were simply controlled by reaction temperature using O2/air as the terminal oxidant and oxygen source. The broad substrate scope, easy realization of gram-scale production, and the simplification of a sulfide oxidation system render the strategy attractive and valuable.
Cheng, Zhen,Sun, Pengchao,Tang, Ailing,Jin, Weiwei,Liu, Chenjiang
supporting information
p. 8925 - 8929
(2019/11/14)

A New Hepta-Nuclear Ti-Oxo-Cluster-Substituted Tungstoantimonate and Its Catalytic Oxidation of Thioethers
A neoteric hepta-nuclear Ti-oxo-cluster-substituted tetrameric tungstoantimonate [H2N(CH3)2]22Na18{Ti7O6(SbW9O33)4}2·124H2O (1) has hydrothermally been synthesized and tested by single-crystal/powder X-ray diffraction, IR spectra, and thermal analysis. The glamorous feature of this tetrameric polyoxoanion is an uncommon hepta-nuclear Ti-oxo-cluster octahedron [Ti7O6]16+ enclosed in four [B-α-SbW9O33]9- building units. As a heterogeneous catalyst, the investigation on catalytic oxidation with H2O2 for multiple thioethers indicated that 1 possesses high conversion and remarkable selectivity. Additionally, 1 exhibits good stability and excellent recyclability.
Li, Hai-Lou,Lian, Chen,Yin, Da-Peng,Jia, Zhi-Yu,Yang, Guo-Yu
p. 376 - 380
(2019/01/09)

Efficient synthesis of 3-benzoyl Benzo[b]thiophenes and raloxifene via Mercury(II)-Catalyzed cyclization of 2-alkynylphenyl alkyl sulfoxides
The unique selective estrogen receptor modulator, Raloxifene (1), and antitubulin agent 2 were synthesized through the key intermediate, 4-methoxybenzyl 2-bromo-4-methoxyphenyl sulfoxide (6), respectively. It was found that compared with the o-sulfanyl aryl bromides, the sulfinyl group at ortho position accelerated the Sonogashira coupling reaction of aryl bromides. Thus, compound 6 was coupled with 3,4,5-trimethoxyphenyl acetylene, followed by mercury-catalyzed cyclization reaction afford compound 2 in 79% overall yield. Raloxifene (1) was prepared from compound 6 in four steps and 33% overall yield via coupling reaction with 1-trimethylsily-2-(4-tert-butyldimethylsiloxy)phenylethyne, mercury-catalyzed cyclization reaction, alkylation and demethylation.
Wen, Shi-Ming,Lin, Cheng-Han,Chen, Chin-Chau,Wu, Ming-Jung
p. 2493 - 2499
(2018/04/16)

Carbazole-triazine based donor-acceptor porous organic frameworks for efficient visible-light photocatalytic aerobic oxidation reactions
We report the synthesis of a series of carbazole-triazine based donor-acceptor (D-A) POFs and their photocatalytic activities for aerobic oxidation reactions. The simultaneous introduction of a carbazole-based electron donor and a triazine-based electron acceptor in D-A POFs stabilizes the charge transfer state and enables an efficient triplet-triplet energy transfer to generate 1O2. Meanwhile, systematic variation of the D-A distance results in the tunable photoredox properties and consequently the efficiency for generation of reactive oxygen species (ROSs). Upon visible light excitation, all three D-A POFs exhibit excellent capability to promote three aerobic oxidations: sulfide oxidation, oxidative amine coupling, and Mannich reactions. This systematic study validates the design principle of D-A POFs as high-performance photo-oxidation catalysts with wide substrate scope and excellent stability and recyclability.
Luo, Jian,Lu, Jingzhi,Zhang, Jian
supporting information
p. 15154 - 15161
(2018/08/17)

A novel catalytic system poly(1-vinyl-3-dodecylimidazolium tribromide)/TBN for the oxidation of sulfides to sulfoxides with air as oxidant
A novel and recoverable polymeric ionic liquid, poly(1-vinyl-3-dodecylimidazolium tribromide) (Poly[VDIM]Br3), was successfully prepared and fully characterized. And a highly efficient metal-free catalytic system Poly[VDIM]Br3/tert-butyl nitrite was developed for the oxidation of sulfides. With air as oxidant, we have successfully achieved 19 kinds of sulfides selectively and efficiently oxidized to corresponding sulfoxides using this catalytic system at room temperature.
Zhang, Hua,Qi, Linlin
p. 3171 - 3174
(2018/07/13)

A highly efficient reusable homogeneous copper catalyst for the selective aerobic oxygenation sulfides to sulfoxides
Readily available copper showed efficient activity and great selectivity for the homogeneous catalysis of oxidation of sulfides to sulfoxides using molecular oxygen as the oxidant. The reaction proceeds under mild conditions in the presence of a catalytic amount of TEMPO. Importantly, the catalysts could be conveniently recovered and reused. And this methodology was proved to be applicable for the transformation of various aromatic and aliphatic sulfides into the corresponding sulfoxides with high conversion and high selectivity.
Ren, Cheng,Fang, Runxing,Yu, Xiaochun,Wang, Shun
supporting information
p. 982 - 986
(2018/02/13)

A recyclable self-assembled composite catalyst consisting of Fe3O4-rose bengal-layered double hydroxides for highly efficient visible light photocatalysis in water
The first case of a highly efficient layered double hydroxide (LDH) supported organic visible light photocatalyst is reported and it can catalyze various organic transformations with high efficiency in water under visible light irradiation.
Huang, Yuxing,Xin, Zhuo,Yao, Wenlong,Hu, Qi,Li, Zhuohua,Xiao, Liuqing,Yang, Bo,Zhang, Junmin
supporting information
p. 13587 - 13590
(2019/01/06)

Amine-functionalized Zn(ii) MOF as an efficient multifunctional catalyst for CO2 utilization and sulfoxidation reaction
Herein, a zinc(ii)-based 3D mixed ligand metal organic framework (MOF) was synthesized via versatile routes including green mechanochemical synthesis. The MOF {[Zn(ATA)(L)·H2O]}n (ZnMOF-1-NH2) has been characterized by var
Patel, Parth,Parmar, Bhavesh,Kureshy, Rukhsana I.,Khan, Noor-Ul H.,Suresh, Eringathodi
supporting information
p. 8041 - 8051
(2018/06/29)

Modular Polyoxometalate–Layered Double Hydroxides as Efficient Heterogeneous Sulfoxidation and Epoxidation Catalysts
The selective sulfoxidation of sulfides and the epoxidation of olefins are two types of important organic reactions, and the corresponding products of sulfoxides, sulfones and epoxides are used widely as raw materials in industrial processes. The fabrication of one efficient catalyst for both reactions remains a challenging task. We report the preparation of a highly efficient heterogeneous catalyst Mg3Al-ILs-La(PW11)2 using an exfoliation/assembly approach. The catalyst was characterised by FT-IR spectroscopy, XRD, thermogravimetric and differential thermal analysis, BET measurements, X-ray photoelectron spectroscopy, 29Si cross-polarisation magic-angle spinning NMR spectroscopy, 27Al magic-angle spinning NMR spectroscopy, SEM, high-resolution TEM, and energy-dispersive X-ray spectroscopy. The designed catalyst showed a high efficiency and selectivity for the sulfoxidation of sulfides and the epoxidation of olefins under mild conditions at a production rate of 208 and 31 mmol g?1 h?1, respectively. Moreover, Mg3Al-ILs-La(PW11)2 can be recycled and re-used at least five times without a clear decrease of its catalytic activity. The scaled-up experiments revealed that the catalyst retained its efficiency and robustness, which demonstrates the great potential of the catalyst for industrial applications.
Li, Tengfei,Zhang, Wei,Chen, Wei,Miras, Haralampos N.,Song, Yu-Fei
p. 188 - 197
(2017/11/28)

Pd/Norbornene Collaborative Catalysis on the Divergent Preparation of Heterocyclic Sulfoximine Frameworks
Pd/Norbornene cocatalyzed tandem C-H activation/annulation reactions of free NH-sulfoximines with aryl iodides to produce diverse polyheterocyclic sulfoximines in highly chemoselective models are reported. The reaction tolerated a broad range of functiona
Zhou, Hao,Chen, Weihao,Chen, Zhiyuan
supporting information
p. 2590 - 2594
(2018/05/17)

Selective photooxidation of sulfides mediated by singlet oxygen using visible-light-responsive coordination polymers
A novel coordination polymer has been synthesized using an anthracene-based linker, and the photocatalytic properties of this visible-light-responsive compound are evaluated where it shows highly selective photooxidation of sulfides to produce sulfoxides relying on reactive species of singlet oxygen.
Liang, Xiao,Guo, Zhifen,Wei, Hongxia,Liu, Xin,Lv, Hui,Xing, Hongzhu
p. 13002 - 13005
(2018/11/23)

Electrochemical synthesis of methyl sulfoxides from thiophenols/thiols and dimethyl sulfoxide
A new route for a one-pot synthesis of methyl sulfoxides from thiophenols/thiols and dimethyl sulfoxide using an electrochemical technique was developed. This protocol proceeded smoothly by employing electrons and hydrogen peroxide as clean oxidants, and a wide range of aromatic and aliphatic sulfoxides were synthesized in moderate to good yields.
Du, Ke-Si,Huang, Jing-Mei
supporting information
p. 1405 - 1411
(2018/03/27)

COMPOUND FOR ORGANIC ELECTRONIC ELEMENT, ORGANIC ELECTRONIC ELEMENT USING THE SAME, AND ELECTRONIC DEVICE THEREOF
Disclosed is an organic electronic element including the compound or the composition as a material for a hole injection layer or a hole transport layer. By using a material including deuterium, with a high driving characteristic and a long life span, it is possible to reduce a driving voltage, and increase a luminous efficiency and a device life span in an organic electro-luminescence element.
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Page/Page column 42; 43

(2017/09/02)

Access to N-cyanosulfoximines by transition metal-free iminations of sulfoxides
A transition metal-free synthesis of N-cyanosulfoximines from sulfoxides using N-chlorosuccinimide (NCS) as oxidising agent and cyanamide as nucleophilic amine source is reported. The products are obtained in moderate to excellent yields. The protocol enables an easy access to N-cyanosulfoximines from readily available starting materials under inversion of configuration at a preexisting stereogenic center.
Dannenberg,Fritze,Krauskopf,Bolm
supporting information
p. 1086 - 1090
(2017/02/10)

Synthesis method of aryl sulfoxide compound
The invention relates to a synthesis method of an aryl sulfoxide compound shown in the following formula (II). The synthesis method comprises the steps as follows: a compound shown in formula (I) is subjected to a catalytic oxidation reaction by using a c
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Paragraph 0079; 0080; 0081; 0082-0084; 0111; 0116; 0121

(2017/07/20)