- Chiral Ligands in Hypervalent Iodine Compounds: Synthesis and Structures of Binaphthyl-Based λ3-Iodanes
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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
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supporting information
(2021/12/22)
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- Aerobic photoxidation of sulfides using unique hybrid polyoxometalate under visible light
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A unique hybrid Polyoxometalate was synthesized, which can absorb visible light and perform photocatalytic activity. This Organic-Inorganic hybrid material was synthesized through attaching the organotin compound to the vacant polyoxometalate. Interesting
- Karimian, Davud,Zangi, Fatemeh
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- Deep eutectic solvent-assisted synthesis of highly efficient nanocatalyst (n-TiO2@TDI@DES (ZnCl2:urea)) for chemoselective oxidation of sulfides to sulfoxides
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This study proposed a straightforward process to synthesize 2,4-toluene diisocyanate (TDI)-functionalized TiO2 nanoparticles in which a cost-effective linker (TDI) with high reactivity was employed to couple nano-TiO2 through covalent bonding to a deep eutectic solvent (DES). By this method, DES was successfully immobilized on the TiO2@TDI surface as an adsorbent and stabilizer. The structural, morphological, and physicochemical characteristics of the synthesized nanocatalysts were evaluated using various analytical methods including Fourier transform infrared (FT-IR) spectroscopy, X-ray diffraction (XRD), thermogravimetric analysis (TGA), scanning electron microscopy equipped with energy-dispersive X-ray spectroscopy (SEM–EDX), and elemental analysis. The heterogeneity of the catalyst was also examined by a hot filtration test. The obtained TiO2@TDI@DES nanoparticles offered superior catalytic behavior and excellent yield as well as recyclability for the chemoselective oxidation of sulfide into sulfoxide using a green oxidant (hydrogen peroxide). This catalyst exhibited excellent reusability as it can be recovered for six successive cycles with no significant leach or reduction of catalytic efficiency.
- Taghavi, Shaghayegh,Amoozadeh, Ali,Nemati, Firouzeh
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- Green synthesis of gold nanoparticles (Au NPs) using Tribulus terrestris extract: Investigation of its catalytic activity in the oxidation of sulfides to sulfoxides and study of its anti-acute leukemia activity
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With regards to applied, facile, green chemical research, a bio-inspired approach is being reported for the synthesis of Au NPs by using Tribulus terrestris extract. The innate oxygenated phytochemicals facilitated the green reduction of Au3+ ions to corresponding NPs and also stabilized them by encapsulating them. This modification prevented the as-synthesized Au NPs towards agglomeration and tiny NPs were obtained in uniformly spherical in shape and in the range of 10–15 nm dimension. Physicochemical characteristics of the green synthesized Au NPs were evaluated by advanced physicochemical techniques like UV–Vis and FT-IR spectroscopy, SEM, TEM, EDX and XRD study. Catalytic performance of the biomolecule functionalized Au NPs was investigated in the controlled and selective oxidation of sulfides to sulfoxides using hydrogen peroxide as green oxidant at room temperature. Aromatic, aliphatic and heterocyclic sulfides were oxidized to their corresponding sulfoxides with high yields without formation of over oxidized sulfones. The catalyst was easily recovered and recycled for 8 successive times without noticeable decrease in catalytic activity. In addition, the biosynthesized Au NPs indicated suitable antioxidant and anti-acute leukemia properties against THP-1 cell line. Tribulus terrestris extract and the green synthesized Au NPs exhibited a maximum DPPH scavenging activity of 78% and 29.37%, respectively. Again, in the anticancer studies over THP-1 cell line following MTT assay, the Au NP exhibited gradual reduced % cell viability with increase in its concentration. At an Au NPs concentration of 2000 μg/mL, the % toxicity became maximum suggesting efficient inhibition of cancer invasion. Based on the above results, Au NPs-Tribulus could be administered as a potential anti-leukemia drug for the treatment of acute leukemia following the clinical trial studies in humans.
- Ahmed, Ahmed Ezzat,El-kott, Attalla,Khames, Ahmed,Zein, Mohamed Abdellatif,Zhao, Peng
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- Green synthesis of Cu/Fe3O4nanocomposite using Calendula extract and evaluation of its catalytic activity for chemoselective oxidation of sulfides to sulfoxides with aqueous hydrogen peroxide
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Plant mediated biogenic synthesizednanoparticles have beenquite familiar as next generation prospective catalysts. In this work, we have demonstrated copper nanoparticles (Cu NP) immobilized magnetic Fe3O4 nanoparticles using Calendu
- Ansari, Siddique Akber,Elgorban, Abdallah M.,Marraiki, Najat,Syed, Asad
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- Catalyst-free visible light-mediated selective oxidation of sulfides into sulfoxides under clean conditions
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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
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supporting information
p. 7945 - 7949
(2021/11/01)
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- New oxovanadium and dioxomolybdenum complexes as catalysts for sulfoxidation: experimental and theoretical investigations of E and Z isomers of ONO tridentate Schiff base ligand
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A new ONO-tridentate Schiff base ligand (H2L) derived by the condensation of nicotinic hydrazide with 5-chlorosalicylaldehyde has been prepared and characterized by combustion analysis (CHN), FT-IR and multinuclear (1H and 13C) NMR spectroscopy. The crystalline nature and molecular structure of the ligand were confirmed by single-crystal X-ray diffraction analysis. Furthermore, the optimized structural parameters of the four possible configurations of the ligand including Z and E stereoisomers each containing two tautomeric forms (enol and keto) have also been investigated. The theoretical parameters were calculated by performing the DFT method using the B3LYP/Def2-TZVP level of theory. In addition to this, dioxomolybdenum(VI) (MoO2L) and oxovanadium(V) (VOL) complexes with the entitled Schiff base ligand have also been prepared and characterized by different techniques. Then, the catalytic efficiencies of synthesized VOL and MoO2L complexes were also explored for the oxidation of sulfides using 30% aqueous H2O2 as a source of oxygen. These homogeneous catalysts showed excellent catalytic activities in the oxidation of both aromatic and aliphatic sulfides.
- Behjatmanesh-Ardakani, Reza,Fallah-Mehrjardi, Mehdi,Kargar, Hadi,Moghimi, Atefeh,Munawar, Khurram Shahzad,Rudbari, Hadi Amiri
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- Efficient Synthesis of Sulfur-Stereogenic Sulfoximines via Ru(II)-Catalyzed Enantioselective C-H Functionalization Enabled by Chiral Carboxylic Acid
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Ru(II)-catalyzed enantioselective C-H functionalization involving an enantiodetermining C-H cleavage step remains undeveloped. Here we describe a Ru(II)-catalyzed enantioselective C-H activation/annulation of sulfoximines with α-carbonyl sulfoxonium ylides using a novel class of chiral binaphthyl monocarboxylic acids as chiral ligands, which can be easily and modularly prepared from 1,1′-binaphthyl-2,2′-dicarboxylic acid. A broad range of sulfur-stereogenic sulfoximines were prepared in high yields with excellent enantioselectivities (up to 99% yield and 99% ee) via desymmetrization, kinetic resolution, and parallel kinetic resolution. Furthermore, the resolution products can be easily transformed to chiral sulfoxides and key intermediates for kinase inhibitors.
- Zhou, Tao,Qian, Pu-Fan,Li, Jun-Yi,Zhou, Yi-Bo,Li, Hao-Chen,Chen, Hao-Yu,Shi, Bing-Feng
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supporting information
p. 6810 - 6816
(2021/05/29)
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- Asymmetric oxidation of sulfides catalyzed by (R)-6,6'-dibromo-BINOL derived titanium complex
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An efficient asymmetric oxidation of sulfides was achieved using (R)-6,6'-dibromo-BINOL as chiral ligand in combination with Ti(OiPr)4 using 70% aqueous tertiary butyl hydroperoxide as oxidant. The resulting sulfoxides had high enantiopurities and good yields. A range of aryl alkyl and aryl benzyl sulfides were oxidized to the corresponding sulfoxides with 78–95% ee in 72–80% yields.
- Maddireddy, Narotham V.,Godbole, Himanshu M.,Singh, Girij P.,Kini, Suvarna G.,Shenoy, Gautham G.
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supporting information
p. 2810 - 2818
(2020/07/13)
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- Localized Partitioning of Enantiomers in Solid Samples of Sulfoxides: Importance of Sampling Method in Determination of Enantiopurity
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Localized partitioning of amorphous enantioenriched aryl benzyl sulfoxides in the solid state can lead to substantial variation in enantiopurities, even for sulfoxides which do not show detectable levels of self-disproportionation of enantiomers (SDE) dur
- Flynn, Aaran J.,Ford, Alan,Maguire, Anita R.
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p. 10216 - 10221
(2020/09/09)
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- Alloxan-catalyzed biomimetic oxidations with hydrogen peroxide or molecular oxygen
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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
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p. 245 - 252
(2019/12/24)
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- Continuous bioinspired oxidation of sulfides
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A simple, efficient, and selective oxidation under flow conditions of sulfides into their corresponding sulfoxides and sulfones is reported herein, using as a catalyst perselenic acid generated in situ by the oxidation of selenium (IV) oxide in a diluted aqueous solution of hydrogen peroxide as the final oxidant. The scope of the proposed methodology was investigated using aryl alkyl sulfides, aryl vinyl sulfides, and dialkyl sulfides as substrates, evidencing, in general, a good applicability. The scaled-up synthesis of (methylsulfonyl)benzene was also demonstrated, leading to its gram-scale preparation.
- Crociani, Letizia,Mangiavacchi, Francesca,Marini, Francesca,Sancineto, Luca,Santi, Claudio
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- Emodinas a novel organic photocatalyst for selective oxidation of sulfides under mild conditions
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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
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p. 19747 - 19750
(2020/06/04)
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- Anchoring Mn(IV) in multi pyridine modified mesoporous silica SBA-15: An efficient nanocatalyst for selective oxidation of sulfides to sulfoxides
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In this current study we report the implementation of Mn(IV) grafted multipyridine linked melanine functionalized SBA-15/CCPy/Mn(OAc)2 as a novel high surface area nanocatalyst. The melamine linked multipyridine ligand was introduced over mesop
- Hekmati, Malak,Hemmati, Saba,Karmakar, Bikash,Salamat, Delafarin,Veisi, Hojat,Yousefi, Mohammad
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- Chiral: N, N ′-dioxide-iron(iii)-catalyzed asymmetric sulfoxidation with hydrogen peroxide
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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
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supporting information
p. 3233 - 3236
(2020/03/23)
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- Highly Efficient Access to (S)-Sulfoxides Utilizing a Promiscuous Flavoprotein Monooxygenase in a Whole-Cell Biocatalyst Format
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Chiral sulfoxides have gained attention as synthons and precursors for API synthesis. Flavoproteins such as Baeyer-Villiger or styrene monooxygenases mainly provide access to (R)-sulfoxides and often suffer from low selectivity, activity, and/or limited substrate scope. The flavoprotein monooxygenase AbIMO from Acinetobacter baylyi ADP1 initiates indole degradation. Here, AbIMO was expressed recombinantly in E. coli and characterized for its sulfoxidation activity and substrate spectrum. Next to indole and styrene, AbIMO was found to accept numerous alkyl aryl sulfides as substrates, transforming them to (S)-sulfoxides with high enantioselectivity (95 percent to '99 percent for most sulfides). The formulation as a whole-cell biocatalyst allowed specific production rates of up to 370 U gcdw?1 – the highest specific oxygenase activity achieved in whole cells so far – and the preparative synthesis of enantiopure (S)-aryl alkyl sulfoxides. With its extraordinarily high specific activity, high specificity, ease of handling, and high stability (catalyst is stable for '16 days at 4 °C), the designed whole-cell biocatalyst adds enormous value to the portfolio of chemical and biological catalysts for asymmetric sulfoxide synthesis.
- Willrodt, Christian,Gr?ning, Janosch A. D.,Nerke, Philipp,Koch, Rainhard,Scholtissek, Anika,Heine, Thomas,Schmid, Andreas,Bühler, Bruno,Tischler, Dirk
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p. 4664 - 4671
(2020/01/22)
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- Metal-free oxidative coupling of alkyl chlorides with thiols: An efficient access to sulfoxides
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An efficient and step-economical access to sulfoxides from thiols and alkyl halides in the presence of I2O5 and DBU via direct oxidative couplings is described here. It is the first case that combined Williamson sulfide synthesis and subsequent sulfide oxidation into one step manipulation for sulfoxides preparation. This protocol features wide substrate scope, mild and metal-free conditons, the use of naturally abundant starting materials and avoidance of over-oxidation.
- Liu, Qian,Zhao, Xiaoqian,Xu, Feng,Li, Gaoqiang
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supporting information
(2019/12/27)
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- A novel binuclear iron(III)-salicylaldazine complex; synthesis, X-ray structure and catalytic activity in sulfide oxidation
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A novel binuclear iron(III)-salicylaldazine complex has been synthesized and characterized by various techniques such as IR and UV–Vis spectroscopy and X-ray crystallography. The catalytic oxidation of sulfides in the presence of the aforementioned complex was explored at room temperature using urea hydrogen peroxide (UHP) as an oxidant. Effects of different reaction conditions consisting catalyst and oxidant amount, solvent effect and reaction time on the catalytic activity and selectivity in the reaction of methylphenylsulfide oxidation has been surveyed. Perfect selectivity toward sulfoxide was achieved after 15 min in CH3CN by choice of a properly optimized reaction condition.
- Akbari, Ali,Amini, Mojtaba,Bagherzadeh, Mojtaba,Ellern, Arkady,Mesbahi, Elnaz,Woo, L. Keith
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- Curbed of molybdenum oxido-diperoxido complex on ionic liquid body of mesoporous Bipy-PMO-IL as a promising catalyst for selective sulfide oxidation
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In this work, we introduce a novel bipyridinium ionic liquid bridged periodic mesoporous organosilicas (Bipy-PMOs-IL) which is used as the support to immobilize oxygen-rich Molybdenum (VI)-based oxido-peroxido complex (MoO(O2)2?Bipy-PMO-IL). Several techniques such as Small-angle X-ray scattering (SAXS), low angle XRD, FE-SEM (field emission scanning electron microscope), TEM (transmission electron microscope), N2 adsorption-desorption analyses (BET), atomic absorption spectroscopy (AAS), Fourier-transform infrared spectroscopy (FT-IR) and Energy Dispersive X-Ray (EDS or EDX) were used to characterize this nanomaterial. Also, the catalytic activities of the MoO(O2)2?Bipy-PMO-IL as a hybrid catalyst is tested in the selective oxidation of sulfides in water by using H2O2 (30%) as an eco-friendly and green co-oxidant. The as-prepared novel catalyst shows high to excellent performance under optimum reaction conditions at ambient room temperature. The obtained results in this work show several outstanding advantages, such as green conditions, high product yields, easy work-up, easy preparation and acceptable reusability of the catalyst for at least 5 runs. To study the IL effect in immobilization of Mo-complex, in a comparison study, the MoO(O2)2?Bipy-PMO-IL materials and MoO(O2)2?SBA-15 (with simple SiO2 body, no IL) body were employed for sulfide oxidation. After the treatment, the Mo?Bipy-PMO-IL with IL body in channels was reused for subsequent experiments (5 runs), but in Mo?SBA-15 after second run the yield was decreased dramatically.
- Ahadi, Arefeh,Dugheri, Stefano,Hasanzadeh, Amir,Kavetskyy, Taras,Khaksar, Samad,Mamba, Bhekie B.,Moaser, Azra Ghiasi,Msagati, Titus A.-M.,Rostamnia, Sadegh,Rouhani, Shamila,Shokouhimehr, Mohammadreza
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- A safe and compact flow platform for the neutralization of a mustard gas simulant with air and light
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A low footprint, mobile, robust and frugal chemical neutralization technology is reported for the oxidative neutralization of a mustard gas simulant. It relies on the inherent properties of a highly engineered continuous flow setup and carefully optimized and simple, yet robust, experimental conditions. The neutralization protocol uses only non-toxic, widely available and cheap chemicals. The continuous flow setup integrates a singlet oxygen generator and exploits its oxidative power to neutralize 2-chloroethyl ethyl sulfide (CEES), the most common thioether mustard gas simulant. The flow reactor can be connected to either pressurized oxygen or air and handles CEES as a 1 M solution in EtOH containing a trace amount (0.06 molpercent) of a non-toxic and widely available photosensitizer (Methylene Blue). Upon irradiation with visible light (orange or white light), total and highly selective neutralization towards the corresponding non-toxic sulfoxide (1-chloro-2-(ethylsulfinyl)ethane, CEESO) is obtained with reactor effluents containing less than 1percent of the corresponding potentially toxic sulfone (1-chloro-2-(ethylsulfonyl)ethane, CEESO2). With a low footprint (L × W × H 94 × 42 × 40 cm), this neutralization technology can be equipped on a vehicle for on-site interventions, localized at a neutralization facility or both. This experimental work is also supported with the computational rationalization of the reactivity of CEES towards singlet oxygen.
- Bianchi, Pauline,Emmanuel, Noémie,Legros, Julien,Monbaliu, Jean-Christophe M.
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supporting information
p. 4105 - 4115
(2020/07/30)
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- Synthesis and nano-Pd catalyzed chemoselective oxidation of symmetrical and unsymmetrical sulfides
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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
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p. 3048 - 3055
(2019/03/21)
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- Fe3O4?BNPs?SiO2-SO3H as a highly chemoselective heterogeneous magnetic nanocatalyst for the oxidation of sulfides to sulfoxides or sulfones
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To achieve green chemistry goals and also to reduce the cost of catalysts as well as to avoid producing toxic wastes and show the importance of separation and recycling of catalysts from the reaction medium, in this work, we describe the preparation and characterization of magnetic acidic boehmite nanoparticles as a heterogeneous catalyst, which is called Fe3O4?BNPs?SiO2-SO3H. This catalyst works efficiently in the selective oxidation of sulfides to sulfoxides or sulfones in the presence of H2O2 as a green oxidant. It can easily be separated from the reaction medium by using an external magnet and it was recycled 6 times without loss of magnetic catalytic properties.
- Ghanbari Kermanshahi, Mohammad,Bahrami, Kiumars
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p. 36103 - 36112
(2019/11/20)
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- Immobilization of Pd(0) complex on the surface of SBA-15: A reusable catalyst for the synthesis of 5-substituted tetrazoles, sulfides and sulfoxides
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A simple and efficient method for the synthesis of 5-substituted tetrazoles, sulfides and sulfoxides in the presence of Pd(0) complex immobilized on mesoporous SBA-15 as an efficient, recoverable and thermally stable mesostructure has been reported. Also, the prepared mesostructure was characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, X-ray mapping, energy-dispersive X-ray spectroscopy, N2 adsorption and desorption, inductively coupled plasma optical emission spectroscopy and thermal gravimetric analysis. Then, this mesostructured catalyst was applied in the synthesis of 5-substituted tetrazoles, sulfides and sulfoxides. The approach described here offers advantages such as short reaction times, high yield, purity yields, simple and eco- friendly, easy work-up. More importantly, this nanohybrid robust catalyst did not undergo metal leaching and applied several times without any decrease in catalytic activity.
- Tamoradi, Taiebeh,Ghorbani-Choghamarani, Arash,Ghadermazi, Mohammad
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p. 374 - 380
(2018/11/01)
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- Water-soluble polymer anchored peroxotitanates as environmentally clean and recyclable catalysts for mild and selective oxidation of sulfides with H2O2 in water
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Anchoring of peroxotitanium (pTi) species to linear water-soluble acrylic acid based polymers, poly(sodium acrylate) (PA) and poly(sodium methacrylate) (PMA) led to the successful synthesis of a pair of new, water-tolerant and recyclable catalysts of the type [Ti2(O2)2O2(OH)2]4-—L (L = PA or PMA), highly effective in chemoselective sulfoxidation of organic sulfides with 30% H2O2 in aqueous medium at ambient temperature. The catalytic protocol is high yielding (TOF up to 11,280 h?1), operationally simple as well as environmentally clean and safe, being free from halide, or any other toxic auxiliaries. The catalysts are sufficiently stable to afford easy recyclability for at least 10 consecutive reaction cycles of sulfoxidation with consistent activity selectivity profile. Oxidation of dibenzothiophene (DBT) to respective high purity sulfoxide or sulfone could also be accomplished using the same catalysts by variation of reaction conditions.
- Ahmed, Kabirun,Saikia, Gangutri,Paul, Sivangi,Baruah, Satyajit Dey,Talukdar, Hiya,Sharma, Mitu,Islam, Nashreen S.
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- Palladium-Catalyzed Enantioselective Alkenylation of Sulfenate Anions
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A novel approach to synthesize enantio-enriched alkenyl/aryl sulfoxides is achieved by using CsF to generate sulfenate anions and conducting the catalytic enantioselective alkenylation with [Pd(allyl)Cl]2/(2R)-1-[(1R)-1-[bis(1,1-dimethylethyl)phosphino]ethyl]-2-(diphenylphosphino)ferrocene (SL-J002-1). A wide variety of sulfoxides bearing sensitive functional groups are produced with high yields (up to 94%) and enantioselectivities (up to 92%).
- Wu, Chen,Berritt, Simon,Liang, Xiaoxia,Walsh, Patrick J.
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supporting information
p. 960 - 964
(2019/05/16)
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- Cercosporin-bioinspired selective photooxidation reactions under mild conditions
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The development of an efficient system for selective oxidation of organic compounds to generate more valuable compounds with molecular oxygen is a significant challenge in industrial chemistry. Bioinspired by the ability of naturally occurring perylenequinonoid pigments (PQPs) to generate reactive oxygen species (ROS) upon photoirradiation, here we report that cercosporin, one of the perylenequinonoid pigments, can function as a cost-effective and environmentally friendly photocatalyst for a wide range of selective oxidations, including benzylic C-H bonds to carbonyls, amines to aldehydes, and sulfides to sulfoxides. All of the representative reactions proceeded smoothly with high efficiency under mild conditions. Owing to the use of inexpensive metal-free visible light-driven photocatalyst produced from microbial fermentation with cheap glucose as the starting material and the ease of handling, we expect that this developed method will be particularly attractive for many more applications in synthetic transformation.
- Li, Jia,Bao, Wenhao,Tang, Zhaocheng,Guo, Baodang,Zhang, Shiwei,Liu, Haili,Huang, Shuping,Zhang, Yan,Rao, Yijian
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supporting information
p. 6073 - 6081
(2019/11/20)
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- Method for synthesizing sulfoxide compound
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The invention discloses a method for synthesizing a sulfoxide compound and belongs to the technical field of synthesis of organic compounds. The method disclosed by the invention comprises the step of catalyzing a reaction between a thioether compound and an oxygen gas agent under the condition of illumination by taking perylene bisimide as a catalyst, thereby obtaining the sulfoxide compound. According to the method, selective oxidation of thioether catalyzed by perylene bisimide under visible light is achieved for the first time, and sulfoxide derivatives are successfully constructed in high yield; and according to the method, the reaction conditions are mild, the reaction efficiency is high, the substrate applicable range is wide, the atom utilization ratio is high, the regioselectivity and chemical selectivity of reaction are high, and thus, the method has a potential application value.
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Paragraph 0103-0107
(2019/10/04)
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- Molybdenum-catalyzed enantioselective sulfoxidation controlled by a nonclassical hydrogen bond between coordinated chiral imidazolium-based dicarboxylate and peroxido ligands
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Chiral alkyl aryl sulfoxides were obtained by molybdenum-catalyzed oxidation of alkyl aryl sulfides with hydrogen peroxide as oxidant in mild conditions with high yields and moderate enantioselectivities. The asymmetry is generated by the use of imidazoli
- Carrasco, Carlos J,Montilla, Francisco,Galindo, Agustín
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- A dichotomy in the enantioselective oxidation of aryl benzyl sulfides: A combined experimental and computational work
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Pentafluorobenzyl pentafluorophenyl sulfide is oxidised with moderate e.e. value and a low yield by the usually highly successful oxidation protocol based upon tert-butyl hydroperoxide (TBHP) in the presence of a titanium/hydrobenzoin complex. This disapp
- Capozzi, Maria Annunziata M.,Bottoni, Andrea,Calvaresi, Matteo,Cardellicchio, Cosimo
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p. 2041 - 2047
(2018/03/21)
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- Ni(II)-Adenine complex coated Fe3O4 nanoparticles as high reusable nanocatalyst for the synthesis of polyhydroquinoline derivatives and oxidation reactions
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In the present study, Fe3O4 nanoparticles were prepared via simple and versatile procedure. Then, a novel and green catalyst was synthesized by the immobilization of Ni on Fe3O4 nanoparticles coated with adenine. The activity of this nanostructure compound was examined for the oxidation of sulfides, oxidative coupling of thiols and synthesis of polyhydroquinolines. The prepared catalyst was characterized by Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), inductively coupled plasma optical emission spectroscopy (ICP-OES), X-ray Diffraction (XRD), thermal gravimetric analysis (TGA), and vibrating sample magnetometer (VSM) measurements. This organometallic catalyst was recovered by the assistance of an external magnetic field from the reaction mixture and reused for seven continuous cycles without noticeable change in its catalytic activity.
- Tamoradi, Taiebeh,Ghadermazi, Mohammad,Ghorbani-Choghamarani, Arash
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- Tungstate supported mesoporous silica SBA-15 with imidazolium framework as a hybrid nanocatalyst for selective oxidation of sulfides in the presence of hydrogen peroxide
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In this work, a new heterogeneous catalyst (SBA-15/Im/WO4 2?) was prepared, and then its performance in the oxidation of organic sulfides was studied (using 30% H2O2 as green oxidant under neutral reaction conditions). This organic–inorganic hybrid mesoporous material was characterized by various techniques, such as FT-IR, inductively coupled plasma, X-ray powder diffraction, high-resolution-transmission electron microscopy, N2 adsorption–desorption and thermogravimetric analysis. The catalyst was also applied to the selective oxidation of various sulfides. The hybrid catalyst was easily recovered, and was very stable and retained good activity for at least five successive runs without any additional activation. Moreover, there was no remarkable decrease in the activity and selectivity of the catalyst. The products could be easily isolated by just removing the solvent after filtering the catalyst. The yields of the catalytic productions through this catalyst were in the range from 75% to 97%.
- Sedrpoushan, Alireza,Hosseini-Eshbala, Fereshteh,Mohanazadeh, Farajollah,Heydari, Masoud
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- Palladium/PC-Phos-Catalyzed Enantioselective Arylation of General Sulfenate Anions: Scope and Synthetic Applications
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Herein we reported an efficient palladium-catalyzed enantioselective arylation of both alkyl and aryl sulfenate anions to deliver various chiral sulfoxides in good yields (up to 98%) with excellent enantioselectivities (up to 99% ee) by the use of our developed chiral O,P-ligands (PC-Phos). PC-Phos are easily prepared in short steps from inexpensive commercially available starting materials. The single-crystal structure of the PC4/PdCl2 showed that a rarely observed 11-membered ring was formed via the O,P-coordination with the palladium(II) center. The salient features of this method include general substrate scope, ease of scale-up, applicable to the late-stage modification of bioactive compounds, and the synthesis of a marketed medicine Sulindac.
- Wang, Lei,Chen, Mingjie,Zhang, Peichao,Li, Wenbo,Zhang, Junliang
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p. 3467 - 3473
(2018/03/13)
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- Transition-Metal-Free Arylations of In-Situ Generated Sulfenates with Diaryliodonium Salts
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A transition-metal-free arylation of sulfenate anions generated from β-sulfinyl esters with diaryliodonium salts was developed. In this process, a new C-S bond is formed under mild reaction conditions providing a wide range of S,S-diaryl and S-alkyl S-aryl sulfoxides.
- Yu, Hao,Li, Zhen,Bolm, Carsten
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supporting information
p. 7104 - 7106
(2018/11/23)
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- Nondirected Copper-Catalyzed Sulfoxidations of Benzylic C-H Bonds
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A copper-catalyzed sulfoxidation of benzylic C-H bonds by nondirected oxidative C(sp3)-H activation was developed. The process proceeds via sulfenate anions, which are generated by base-triggered elimination of β-sulfinyl esters and benzyl radicals. The functional group tolerance is high, and the product yields are good.
- Yu, Hao,Li, Zhen,Bolm, Carsten
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supporting information
p. 2076 - 2079
(2018/04/16)
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- One-pot synthesis of α-phenylsulfinyl ketones by reaction of phenyl benzenethiosulfinate with enolate anions, and synthesis of sulfoxides and sulfides by its reaction with Grignard reagents
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Phenyl benzenethiosulfinate reacts with enolate anions derived from ketones to give α-phenylsulfinyl ketones directly, together with minor amounts of α-phenylsulfanyl ketones. These are easily separated by forming the water-soluble sodium salts of the sulfinyl compounds. Grignard reagents also react with phenyl benzenethiosulfinate, to give mixtures of sulfoxides and sulfides.
- Fakhry, Jerome,Grayson, David H.
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p. 556 - 563
(2017/12/28)
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- Aryl sulfoxide, thioether compound, synthesis method and application thereof
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The invention discloses a method for selective synthesis of an aryl sulfoxide compound (III) and an aryl thioether compound (IV). According to the invention, in a reactive solvent, an aryl high iodinesalt is adopted as the reaction raw material, aryl/alkyl thiosulfate is taken as the vulcanizing reagent, under the catalysis of visible light and a photosensitive reagent, and under the action of lewis acid and alkali, when the reaction atmosphere is nitrogen, the thioether compound (IV) can be generated, and when the reaction atmosphere is air, the sulfoxide compound (III) can be generated. Thesynthesis method provided by the invention has the advantages of easily available and cheap raw materials, simple reaction operation, mild and environment-friendly reaction conditions, high yield, and excellent functional group tolerance. The invention also discloses the new aryl sulfoxide compound (III) and aryl thioether compound (IV), also successfully realizes later modification of drugs andsugar, and realizes the formal synthesis of some drugs, and provides an efficient method for selective construction of thioether and sulfoxide compounds.
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Paragraph 0110-0113
(2018/04/21)
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- Synthesis of: N -alkylated 2-pyridones through Pummerer type reactions of activated sulfoxides and 2-fluoropyridine derivatives
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N-Alkylated 2-pyridone products were obtained in good to excellent yields through a one-pot procedure involving either normal or interrupted Pummerer reactions between triflic anhydride activated sulfoxides and 2-fluoropyridine derivatives, followed by hydrolysis. This is a rare case that uses 2-fluoropyridine as a nucleophile in Pummerer type reactions.
- Hu, Gang,Xu, Jiaxi,Li, Pingfan
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p. 4151 - 4158
(2018/06/12)
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- Synthesis of new oxido-vanadium complexes: Catalytic properties and cytotoxicity
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Reaction of 2,3-dihydroxy benzaldehyde with 2-({2-amino phenyl}diazenyl)phenol afforded the ligand 3-(2-(2-hydroxyphenyl)diazenyl)- 4-alkylphenyliminomethyl)benzene-1,2-diol. Reaction of H2L with VOSO4. 5H2O gave the oxido-vanadium(IV) complexes [(L)VO], which exhibited a quasi-reversible oxidative cyclic voltammetric response in a V(IV)/V(V) oxidative process. The complexes act as catalysts in the oxidation of organic thioethers and bromination of phenol. Their cytotoxic properties were examined for three cancer cell lines.
- Das, Uttam,Pattanayak, Poulami,Santra, Manas Kumar,Chattopadhyay, Surajit
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- Synthesis, characterization, spectral and catalytic activity of tetradentate (NNNO) azo-imine Schiff base copper(II) complexes
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The hexadentate ligand, 2,2′-bis(salicylideneamino)azobenzene, 1 has been synthesized from 2,2′-diaminoazobenzene and salicylaldehyde in refluxing diethyl ether. Reaction of ligand 1 with Cu(II) acetate and Cu(II) perchlorate separately in methanol afforded tetradentate (N,N,N,O) Cu(II) complexes, Cu(L) & [Cu(HL)]ClO4 respectively [where H2L represent the one imine moiety cleavage product of ligand 1 (H represents the dissociable amino and phenolic protons)]. These were characterized by microanalytical data and spectroscopic studies. In addition, the crystal structures of the ligand 1 and complexes Cu(L) & [Cu(HL)]ClO4 were determined by X-ray diffraction analysis. The diffraction analysis revealed that the ligand (H2L) binds Cu(II) centers in (N,N,N,O) tetra dentate fashion in distorted square planer geometry. In complex [Cu(HL)]ClO4 the apical position of copper center is weakly coordinated with one perchlorate ion. The dimeric structure of the molecule [Cu(HL)]ClO4 is stabilized through NH2···O hydrogen bonds. The fluorescence and redox property of ligand 1 and complexes Cu(L) & [Cu(HL)]ClO4 were studied. Preliminary DFT calculations were carried out using crystallographic coordinates to understand the electronic spectra and redox properties of the ligand and complexes. The complex Cu(L) shows very good catalytic activities towards oxidation of benzyl alcohol to benzaldeyhde (under solvent-free condition) and organic thioethers to sulfoxide and sulfones using H2O2 as the oxidant.
- Pratihar, Jahar Lal,Mandal, Paritosh,Brand?o, Paula,Mal, Dasarath,Felix, Vitor
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p. 221 - 228
(2018/05/22)
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- Oxido-peroxido W(VI)-histidine–MgAl-layered double hydroxide composite as an efficient catalyst in sulfide oxidation
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Oxido-peroxido W(VI)-histidine–MgAl-layered double hydroxide composite was prepared by using MgAl-layered double hydroxide as a host and oxido-peroxido W(VI)-histidine complex as a guest. The composite was characterized by XRD, IR, EDX,SEM and TEM techniques. This composite is tested for catalytic selective sulfoxidation reactions using hydrogen peroxide as oxidant showing good to moderate conversion along with high selectivity.
- Nikkhoo, Mohammad,Amini, Mojtaba,Morteza,Farnia,Bayrami, Arshad,Bagherzadeh, Mojtaba,Gautam, Sanjeev,Chae, Keun Hwa
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- An efficient silica supported Chitosan@vanadium catalyst for asymmetric sulfoxidation and its application in the synthesis of esomeprazole
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A new type of silica supported Chitosan@vanadium complex was used as a highly active heterogeneous catalyst for asymmetric oxidation of aryl alkyl sulfides. With the economic aqueous H2O2(30%) as the oxidant, the oxidation products were obtained in high yields (up to 95%) with good enantioselectivities (up to 68% ee). It is noted that the marketed drug Nexium (first proton-pump inhibitor, esomeprazole) could be synthesized easily by the newly developed asymmetric sulfoxidation reaction. In addition, the highly active catalyst can be reused five times without losing its catalytic activity.
- Shen, Chao,Qiao, Jun,Zhao, Linwei,Zheng, Kai,Jin, Jianzhong,Zhang, Pengfei
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p. 114 - 118
(2017/01/25)
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- Sulfoxidation inside a C3-vanadium(V) bowl-shaped catalyst
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The confined enantiopure oxido-vanadium complex SSS-RRR-1 was synthesized and tested as a catalyst for the oxidation of sulfides into sulfoxides. This catalyst is very efficient with a reaction rate more than 300 times higher than that of the model compound SSS-RRR-3, and a turnover number (TON) close to 105 was reached in combination with a good selectivity (more than 90%) in the sulfoxide product. Moreover, enantiomerically enriched sulfoxide can be obtained, breaking through the major limitation of the previous chiral vanatrane catalysts that show no detectable enantiomeric excess (ee). Further investigations revealed that the complex SSS-RRR-1 adopts a bowl-shaped structure with an open hydrophobic pocket. The microenvironment of the chiral pocket above the metal center accounts for the strong improvement in catalytic activity and enantioselectivity.
- Zhang, Dawei,Dutasta, Jean-Pierre,Dufaud, Veronique,Guy, Laure,Martinez, Alexandre
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p. 7340 - 7345
(2017/11/09)
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- Intermolecular Pummerer Coupling with Carbon Nucleophiles in Non-Electrophilic Media
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A new Pummerer-type C?C coupling protocol is introduced based on turbo-organomagnesium amides, which unlike traditional Pummerer reactions, does not require strong electrophilic activators, engages a broad range of C(sp3)-, C(sp2)-, and C(sp)-nucleophiles, and seamlessly integrates with C?H and C?X magnesiation. Given the central character of sulfur compounds in organic chemistry, this protocol allows access to unrelated carbonyls, olefins, organometallics, halides, and boronic esters through a single strategy.
- Colas, Kilian,Martín-Montero, Raúl,Mendoza, Abraham
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p. 16042 - 16046
(2017/11/21)
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- Metal- and additive-free oxygen-atom transfer reaction: an efficient and chemoselective oxidation of sulfides to sulfoxides with cyclic diacyl peroxides
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Metal- and additive-free oxidation of a series of sulfides/thioketones has been achieved using cyclic diacyl peroxides as mild oxygen sources. This protocol features simple manipulation, high chemo- and diastereoselectivity, and a broad substrate scope (up to 42 examples), tolerates many common functional groups, and is scalable and applicable to the late-stage sulfoxidation strategy. A preliminary mechanistic study by quantum mechanical calculations suggests that a single two-electron transfer process is energetically more favorable, and indicates the reactivity of cyclic diacyl peroxides distinct from conventional acyclic acyl peroxides.
- Gan, Shaoyan,Yin, Junjie,Yao, Yuan,Liu, Yang,Chang, Denghu,Zhu, Dan,Shi, Lei
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supporting information
p. 2647 - 2654
(2017/04/03)
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- A Mild, Efficient and Highly Selective Oxidation of Sulfides to Sulfoxides Catalyzed by Lewis Acid–Urea–Hydrogen Peroxide Complex at Room Temperature
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Alkyl and aryl sulfides were oxidized to the corresponding sulfoxides with urea–hydrogen peroxide (UHP) in the presence of FeCl3 as a Lewis acid catalyst under simple and mild reaction conditions. The protocol is efficient and highly selective
- Azizi, Mojtaba,Maleki, Ali,Hakimpoor, Farahman,Ghalavand, Reza,Garavand, Ali
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p. 2173 - 2177
(2017/07/25)
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- Method for catalyzing asymmetric oxidation of sulfur ether
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The invention provides a method for asymmetrically oxidizing sulfur ether. The sulfur ether is subjected to asymmetric catalytic oxidation reaction by taking a chiral complex formed by a four-tooth nitrogen organic ligand and a metal scandium compound as a catalyst and taking hydrogen peroxide as an oxidizing agent to obtain a corresponding chiral sulfoxide compound, and the yield and the enantioselectivity are more than 90 percent. The reaction has the advantages of cleanness, mild reaction condition, high conversion rate and high enantioselectivity. The method has an industrial prospect.
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Paragraph 0028; 0029; 0030; 0031
(2017/08/30)
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- Enantioselective Aromatic Sulfide Oxidation and Tandem Kinetic Resolution Using Aqueous H2O2 and Chiral Iron–Bis(oxazolinyl)bipyridine Catalysts
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An efficient method for the oxidation of aromatic sulfides has been developed by using aqueous H2O2, catalyzed by the in situ generated chiral Fe/6,6′-bis(4-isopropyloxazolin-2-yl)-2,2′-bipyridine (bipybox-iPr) complex. The corresponding sulfoxides were obtained with high enantioselectivities (up to 98.5:1.5 er) and in good yields (up to 61 %) when the mono-oxidation of the sulfides was performed in combination with the kinetic resolution of the sulfoxide into the sulfone.
- Jalba, Angela,Régnier, Noémie,Ollevier, Thierry
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p. 1628 - 1637
(2017/04/06)
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- Nickel-Catalyzed Cross-Coupling Reaction of Aryl Sulfoxides with Arylzinc Reagents: When the Leaving Group is an Oxidant
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Nickel-catalyzed Negishi-type cross-coupling of aryl methyl sulfoxides with arylzinc reagents has been developed. By consuming the catalyst-oxidizing methanesulfenate anion through oxidative homocoupling of the arylzinc reagent, smooth catalyst turnover c
- Yamamoto, Keita,Otsuka, Shinya,Nogi, Keisuke,Yorimitsu, Hideki
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p. 7623 - 7628
(2017/11/14)
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- Controllable Sulfoxidation and Sulfenylation with Organic Thiosulfate Salts via Dual Electron- and Energy-Transfer Photocatalysis
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Sulfoxides and sulfides are two important functional groups in organic molecules, containing different valence states of sulfur. Both sulfoxidation and sulfenylation with common sulfurating reagents were successfully tuned via a facile variation of the atmosphere under photocatalyzed conditions. The sulfoxidation and sulfenylation transformations involved tandem electron-/energy-transfer and single-electron-transfer processes, respectively. Late-stage sulfoxidation for pharmaceuticals and sugar derivatives was established to be highly compatible. Divergent formal syntheses of sulfoxide/sulfide-containing marketed pharmaceuticals were switchably implemented. Gram-scale operations further demonstrated the practicability of the protocol.
- Li, Yiming,Wang, Ming,Jiang, Xuefeng
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p. 7587 - 7592
(2017/11/10)
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