- Practical synthesis of active O-2-(2-propylsulfinyl)benzyl (OPSB) glycosides via a catalytic and metal free oxidation of latent O-2-(2-propylthiol)benzyl (OPTB) glycosides
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A catalytic and metal free sulfoxidation of O-2-(2-propylthiol)benzyl (OPTB) glycosides to O-2-(2-propylsulfinyl)benzyl (OPSB) glycosides has been developed by introducing NOBF4 as catalyst, oxygen as terminal oxidant and TBAB as additive. Wide
- Xiao, Ying,Lu, Zimin,Zhao, Xiang,Wu, Pingru,Chen, Wei,Wang, Ruobing,Zeng, Jing,Wan, Qian
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- Magnetically recoverable heterogeneous catalyst: Tungstate intercalated Mg-Al-layered double hydroxides-encapsulated Fe3O4 nanoparticles for highly efficient selective oxidation of sulfides with H 2O2
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High catalytic activity of tungstate intercalated in hydrotalcite- encapsulated magnetic Fe3O4 nanoparticles have been prepared. High resolution transmission electron microscopy characterization demonstrated the formation of Fe3
- Yuan, Chengyuan,Liu, Honghai,Gao, Xionghou
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- Micellar catalysis on the electron transfer reactions of iron(III)-polypyridyl complexes with organic sulfides - Importance of hydrophobic interactions
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The oxidation of organic sulfides with iron(iii)-polypyridyl complexes [Fe(NN)3]3+ proceeds through an electron transfer mechanism and an increase in the methanol content in the methanol-water mixture favors the reaction. The reactio
- Balakumar,Thanasekaran,Rajkumar,Adaikalasamy, K. John,Rajagopal,Ramaraj,Rajendran,Manimaran,Lu
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- Sulfoxide and Sulfone Synthesis via Electrochemical Oxidation of Sulfides
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The oxidation of diaryl sulfides and aryl alkyl sulfides to the corresponding sulfoxides and sulfones under electrochemical conditions is reported. Sulfoxides are selectively obtained in good yield under a constant current of 5 mA for 10 h in DMF, while sulfones are formed as the major product under a constant current of 10 or 20 mA for 10 h in MeOH. The oxygen of both the sulfoxide and sulfone function is derived from water.
- Lee, Sunwoo,Park, Jin Kyu
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p. 13790 - 13799
(2021/10/12)
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- Selective Catalytic Oxidation of Organic Sulfides to Sulfoxides without Forming Sulfones over Solid Molybdenum Blue: Kinetic and Thermodynamic Studies
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The present investigation reports studies on the selective catalytic oxidation of organic sulfide substrates over molybdenum blue catalyst supported on boron phosphate. The catalyst was synthesized through partial precipitation method and characterized by
- Ratheshkumar,Induja,Raghavan
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p. 2267 - 2274
(2020/09/16)
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- Exploiting Substrate Diversity for Preparing Synthetically Valuable Sulfoxides via Asymmetric Hydrogenative Kinetic Resolution
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A detailed study is disclosed on the Rh-mediated hydrogenative kinetic resolution of α,β-unsaturated sulfoxides with alkyl and aryl substituents at the α-, E- and Z-positions of the double bond. This stereoselective catalytic methodology has enabled the p
- Fernández-Pérez, Héctor,Grabulosa, Arnald,Lao, Joan R.,Vidal-Ferran, Anton
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supporting information
(2020/07/24)
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- Polymer-supported eosin Y as a reusable photocatalyst for visible light mediated organic transformations
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A novel polymer-supported recyclable photocatalyst has been developed for visible light mediated oxidation reactions. The organic dye eosin Y was loaded on macroporous commercially available Amberlite IRA 900 chloride resin and exploited as a photocatalyst for visible light mediated oxidation of thioethers to sulfoxides and phenylboronic acids to phenols under open atmospheric air. Varieties of functional groups were well tolerated during oxidation. The catalyst is recyclable for six cycles without significant loss in its efficiency. Furthermore, gram-scale oxidation of sulfides to sulfoxides has been demonstrated to prove the commercial viability of the method.
- Sridhar, Arunasalam,Rangasamy, Rajmohan,Selvaraj, Mari
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p. 17974 - 17979
(2019/12/02)
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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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- Enantioseparation of Sulfoxides and Nitriles by Inclusion Crystallization with Chiral Organic Salts Based on l-Phenylalanine
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Enantioselective inclusion of aromatic sulfoxides and nitriles was achieved in a host framework created by organic salts comprising achiral benzoic acids and a chiral primary amine (1a) derived from l-phenylalanine. Tuning of the combined achiral acid component successfully changed the chiral recognition ability of the organic salts. The guest molecules were hydrogen-bonded to form three-component inclusion crystals, and the enantiomers of nitriles and sulfoxides were separated with high selectivity up to 92 and 98 % ee. As far as we know, this is the first example of the enantioseparation of non-functionalized aromatic nitriles.
- Kodama, Koichi,Kanai, Hayato,Shimomura, Yuki,Hirose, Takuji
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supporting information
p. 1726 - 1729
(2018/04/24)
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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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supporting information
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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- Asymmetric Sulfinylations of N-Methylephedrine-Modified Tri- or Tetraalkyl Zincates by Symmetric Diaryl Sulfoxides
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Diethylzinc was treated with 1 or 2 equiv. of AlkMgCl or PhMgBr (preferably) or with 1 equiv. of nBuLi (less efficiently) for forming species – plausibly zincates – which were sulfinylated by diaryl sulfoxides to give racemic alkyl aryl sulfoxides in yields reaching 100 %. Dialkylzinc reagents were also activated by treatments with 1 or 2 equiv. of an enantiomerically pure alkylmagnesium β-aminoalkoxide. This worked best when the alkoxide stemmed from a dialkylmagnesium reagent and an equimolar amount of N-methyl-(–)-ephedrine. This second activation mode allowed sulfinylations of what was originally the dialkylzinc reagent with diaryl sulfoxides. This generated alkyl aryl sulfoxides with enantiomeric ratios up to 93:7 in up to 100 % yield.
- Ruppenthal, Simon,Brückner, Reinhard
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p. 2518 - 2530
(2018/06/11)
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- Multivariate Metal-Organic Frameworks as Multifunctional Heterogeneous Asymmetric Catalysts for Sequential Reactions
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The search for versatile heterogeneous catalysts with multiple active sites for broad asymmetric transformations has long been of great interest, but it remains a formidable synthetic challenge. Here we demonstrate that multivariate metal-organic frameworks (MTV-MOFs) can be used as an excellent platform to engineer heterogeneous catalysts featuring multiple and cooperative active sites. An isostructural series of 2-fold interpenetrated MTV-MOFs that contain up to three different chiral metallosalen catalysts was constructed and used as efficient and recyclable heterogeneous catalysts for a variety of asymmetric sequential alkene epoxidation/epoxide ring-opening reactions. Interpenetration of the frameworks brings metallosalen units adjacent to each other, allowing cooperative activation, which results in improved efficiency and enantioselectivity over the sum of the individual parts. The fact that manipulation of molecular catalysts in MTV-MOFs can control the activities and selectivities would facilitate the design of novel multifunctional materials for enantioselective processes.
- Xia, Qingchun,Li, Zijian,Tan, Chunxia,Liu, Yan,Gong, Wei,Cui, Yong
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supporting information
p. 8259 - 8266
(2017/06/28)
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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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- Catalyst-free oxidation of sulfides to sulfoxides and diethylamine catalyzed oxidation of sulfides to sulfones using Oxone as an oxidant
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Abstract: We describe here our journey from the failure of our attempts in controlled oxidation of sulfides to sulfoxides using an Oxone–KBr combination to our success in the development of a catalyst-free protocol for the oxidation of sulfides to sulfoxides using Oxone as an oxidant. We also describe the failure of our attempts at the oxidation of sulfides to sulfones using an excess of Oxone–KBr as well as Oxone, and our success towards the development of a rapid, scalable and chromatography-free protocol for the oxidation of sulfides to sulfones using diethylamine–Oxone as an unprecedented catalyst–oxidant combination.
- Kupwade,Khot,Lad,Desai,Wadgaonkar
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p. 6875 - 6888
(2017/10/06)
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- Exploiting a beast in carbenoid chemistry: Development of a straightforward direct nucleophilic fluoromethylation strategy
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The first direct and straightforward nucleophilic fluoromethylation of organic compounds is reported. The tactic employs a fleeting lithium fluorocarbenoid (LiCH2F) generated from commercially available fluoroiodomethane. Precise reaction conditions were developed for the generation and synthetic exploitation of such a labile species. The versatility of the strategy is showcased in ca. 50 examples involving a plethora of electrophiles. Highly valuable chemicals such as fluoroalcohols, fluoroamines, and fluoromethylated oxygenated heterocycles could be prepared in very good yields through a single synthetic operation. The scalability of the reaction and its application to complex molecular architectures (e.g., steroids) are documented.
- Parisi, Giovanna,Colella, Marco,Monticelli, Serena,Romanazzi, Giuseppe,Holzer, Wolfgang,Langer, Thierry,Degennaro, Leonardo,Pace, Vittorio,Luisi, Renzo
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supporting information
p. 13648 - 13651
(2017/11/06)
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- Chiral DHIP-Based Metal-Organic Frameworks for Enantioselective Recognition and Separation
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Two chiral porous 2,3-dihydroimidazo[1,2-a]pyridine (DHIP)-based metal-organic frameworks (MOFs) are assembled from an enantiopure dipyridyl-functionalized DHIP bridging ligand. The Zn-DHIP MOF shows a good enantioseparation performance toward aromatic sulfoxides, and the heterogeneous adsorbent can be readily recovered and reused without significant degradation of the separation performance.
- Zhang, Jie,Li, Zijian,Gong, Wei,Han, Xing,Liu, Yan,Cui, Yong
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supporting information
p. 7229 - 7232
(2016/08/09)
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- A chemoselective oxidation of sulfides to sulfoxides and sulfones using urea-2,2-dihydroperoxypropane as a novel oxidant
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Background: Sulfoxides and sulfones have been in the center of attention due to their wide range of promises in various approaches. The functional groups presented in these compounds serve as important building blocks in numerous natural, pharmeceutical and agricultural compounds. These deriatives have been prepared through a multitude of routes which were accompanied by several drawbacks. Therefore, there has been an ever-increasing interest to find a new methodology that leads to the production of these compounds via an environmentally benign path bringing about high yields. Recently, gem-dihydroperoxides have attracted much attention due to their oxidizing power and they have been utilized in several oxidation processes. Methods: We carried out a chemoselective oxidation of sulfides to sulfoxides and sulfones on treatment with urea-2,2-dihydroperoxypropane, a solid oxidant composed of equal amounts of 2,2-dihydroperoxypropane and urea, using THF as the solvent under catalyst-free conditions at room temprature. Results: Sulfides possessing a variety of substitutions namely dialkyl, diaryl, ally l and alkyl-aryl were subjected to the optimized reaction conditions and they could successfully afford different amounts of sulfoxides and sulfones depending on the amount of the oxidant utilized. Based on the results, electron-donating groups accelerated the reaction while electron-withdrawing substituents lowered the reactivity. Conclusion: Urea-2,2-dihydroperoxypropane as a solid oxidant which can be stored for several months without any loss in its activity has proved its capability to oxidize sulfides to sulfoxides and sulfones under catalyst-free and mild conditions. This approach is a cost-effective and environmentally benign methodology via which the products have been synthesized in high yields and short reaction times.
- Khosravi, Kaveh,Naserifar, Shirin,Asgari, Atefeh
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p. 749 - 756
(2017/02/05)
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- Metal-free chemoselective oxidation of sulfides to sulfoxides catalyzed by immobilized l-aspartic acid and l-glutamic acid in an aqueous phase at room temperature
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l-Aspartic acid and l-glutamic acid were immobilized on hybrid silica and characterized by FT-IR, XPS, contact angle measurements, TGA, SEM and XRD. Employed as heterogeneous catalysts in the selective oxidation of sulfides with 30% H2O2 at room temperature, 99% conversion and 97% selectivity were achieved with excellent substrate tolerance and recyclability.
- Shen, Hai-Min,Zhou, Wen-Jie,Yu, Wu-Bin,Wu, Hong-Ke,Liu, Qiu-Ping,Ji, Hong-Bing,Wang, Yan,She, Yuan-Bin
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supporting information
p. 4874 - 4878
(2016/07/06)
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- Formation of Ternary Inclusion Crystal and Enantioseparation of Alkyl Aryl Sulfoxides by the Salt of Urea-Modified l -Phenylalanine and an Achiral Amine
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Chiral supramolecular hosts comprising urea-modified l-phenylalanines and achiral primary amines were developed, which facilitated enantioselective inclusion of alkyl aryl sulfoxides (3) up to 89% ee owing to the formation of ternary inclusion crystals. F
- Kodama, Koichi,Morita, Rina,Hirose, Takuji
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p. 5206 - 5213
(2016/11/05)
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- pH-dependence of the aqueous phase room temperature Br?nsted acid-catalyzed chemoselective oxidation of sulfides with H2O2
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A pH-dependence of the Br?nsted acid-catalyzed oxidation of sulfides to the corresponding sulfoxides with H2O2 is reported for the first time based on our systematic investigation of the catalytic performance of a series of Br?nsted acids. For all of the Br?nsted acids investigated, the catalytic performances do not depend on the catalyst loading (mol ratio of Br?nsted acid to substrate), but rather depend on the pH value of the aqueous reaction solution. All of them can give more than 98% conversion and selectivity in their aqueous solution at pH 1.30, no matter how much the catalyst loading is and what the Br?nsted acid is. This pH-dependence principle is a very novel perspective to understand the Br?nsted-acid catalysis system compared with our common understanding of the subject.
- Shen, Hai-Min,Zhou, Wen-Jie,Ma, Xin,Wu, Hong-Ke,Yu, Wu-Bin,Ai, Ning,Ji, Hong-Bing,Shi, Hong-Xin,She, Yuan-Bin
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p. 16709 - 16722
(2015/12/01)
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- Palladium-Catalyzed Arylation of Alkyl Sulfenate Anions
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A unique palladium-catalyzed arylation of alkyl sulfenate anions is introduced that affords aryl alkyl sulfoxides in high yields. Due to the base sensitivity of the starting sulfoxides, sulfenate anion intermediates, and alkyl aryl sulfoxide products, the use of a mild method to generate alkyl sulfenate anions was crucial to the success of this process. Thus, a fluoride triggered elimination strategy was employed with alkyl 2-(trimethylsilyl)ethyl sulfoxides to liberate the requisite alkyl sulfenate anion intermediates. In the presence of palladium catalysts with bulky monodentate phosphines (SPhos and Cy-CarPhos) and aryl bromides or chlorides, alkyl sulfenate anions were readily arylated. Moreover, the thermal fragmentation and the base promoted elimination of alkyl sulfoxides was overridden. The alkyl sulfenate anion arylation exhibited excellent chemoselectivity in the presence of functional groups, such as anilines and phenols, which are also known to undergo palladium catalyzed arylation reactions.
- Jia, Tiezheng,Zhang, Mengnan,Jiang, Hui,Wang, Carol Y.,Walsh, Patrick J.
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supporting information
p. 13887 - 13893
(2016/01/15)
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- Tert-Butyl Sulfoxide as a Starting Point for the Synthesis of Sulfinyl Containing Compounds
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Sulfoxides bearing a tert-butyl group can be activated using N-bromosuccinimide (NBS) under acidic conditions and then subsequently treated with a variety of nitrogen, carbon, or oxygen nucleophiles to afford a wide range of the corresponding sulfinic acid amides, new sulfoxides, and sulfinic acid esters.
- Wei, Juhong,Sun, Zhihua
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supporting information
p. 5396 - 5399
(2015/11/18)
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- Copper-Schiff base complex catalyzed oxidation of sulfides with hydrogen peroxide
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A straightforward, efficient, and selective oxidation of sulfide to sulfoxide with 30% H2O2 catalyzed by copper(II)-Schiff base complex is described. The reactions proceed under mild conditions in acetonitrile at room temperature to provide a variety of aryl and alkyl sulfoxides in excellent yield.
- Gogoi, Prasanta,Kalita, Mukul,Bhattacharjee, Tirtha,Barman, Pranjit
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p. 1028 - 1030
(2014/02/14)
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- Copper-Schiff base complex catalyzed oxidation of sulfides with hydrogen peroxide
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A straightforward, efficient, and selective oxidation of sulfide to sulfoxide with 30% H2O2 catalyzed by copper(II)-Schiff base complex is described. The reactions proceed under mild conditions in acetonitrile at room temperature to provide a variety of aryl and alkyl sulfoxides in excellent yield.
- Gogoi, Prasanta,Kalita, Mukul,Bhattacharjee, Tirtha,Barman, Pranjit
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supporting information
p. 1028 - 1030
(2015/02/05)
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- Nickel ferrite nanoparticles-hydrogen peroxide: A green catalyst-oxidant combination in chemoselective oxidation of thiols to disulfides and sulfides to sulfoxides
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Nickel ferrite nanoparticles-hydrogen peroxide has been demonstrated for the first time as a green and efficient catalyst-oxidant combination in the chemoselective oxidation of thiols to disulfides and sulfides to sulfoxides. This magnetically separable catalyst was found to be reusable for five consecutive runs without appreciable change in the activity, as well as composition of the catalyst. The mechanism for the oxidation of thiols and sulfides has also been proposed. the Partner Organisations 2014.
- Kulkarni, Aparna M.,Desai, Uday V.,Pandit, Kapil S.,Kulkarni, Makarand A.,Wadgaonkar, Prakash P.
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p. 36702 - 36707
(2014/12/10)
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- Ion pairs of weakly coordinating cations and anions: Synthesis and application for sulfide to sulfoxide oxidations
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A series of salts containing the weakly coordinating cations (WCC) 1-butyl-3-methylimidazolium ([Bmim]+), 1-butyl-2,3-dimethylimidazolium ([Bdmim]+), 1-dodecyl-3-methylimidazolium ([C12mim]+), tetrabutylphosphonium ([PBu4]+), tributyltetradecyl
- Zhang, Bo,Li, Su,Cokoja, Mirza,Herdtweck, Eberhardt,Mink, Jnos,Zang, Shu-Liang,Herrmann, Wolfgang A.,Kühn, Fritz E.
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p. 1149 - 1163
(2015/06/16)
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- Oxidation of organic sulfides by imidazolium fluorochromate: A kinetic and mechanistic approach
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The oxidation of organic sulfides by imidazolium fluorochromate resulted in the formation of the corresponding sulfoxides. The reaction is first order with respect to imidazolium fluorochromate. A Michaelis-Menten type kinetics was observed with respect t
- Mathur, Lokesh,Choudhary,Prakash, Om,Sharma, Pradeep K.
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p. 2597 - 2603
(2014/06/09)
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- Kinetics and correlation analysis of reactivity in the oxidation of some alkyl phenyl sulfides by benzimidazolium dichromate
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The oxidation of some alkyl phenyl sulfides by benzimidazolium dichromate (BIDC) in dimethyl sulfoxide, to the corresponding sulfoxides, is first order with respect to BIDC. Michaelis-Menten type kinetics was observed with respect to sulfide. Thermodynami
- Pandey, Dinesh,Kothari, Seema
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p. 1224 - 1230
(2015/02/19)
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- Engineering chiral Fe(salen)-based metal-organic frameworks for asymmetric sulfide oxidation
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Two chiral porous Fe(salen)-based metal-organic frameworks are constructed and are shown to be efficient and recyclable heterogeneous catalysts for asymmetric oxidation of sulfides to sulfoxides with an enantioselectivity of up to 96%.
- Yang, Zhiwei,Zhu, Chengfeng,Li, Zijian,Liu, Yan,Liu, Guohua,Cui, Yong
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p. 8775 - 8778
(2014/07/22)
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- Diastereoconvergent synthesis of trans -5-hydroxy-6-substituted-2- piperidinones by addition-cyclization-deprotection process
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A diastereoselective one-pot approach to access trans-5-hydroxy-6- substituted-2-piperidinones by an addition-cyclization-deprotection process has been developed, in which the stereogenic center at the C-6 position was solely controlled by α-OTBS group. The utility of this transformation is demonstrated by the asymmetric synthesis of the enantiomer of (-)-CP-99,994.
- Si, Chang-Mei,Huang, Wei,Du, Zhen-Ting,Wei, Bang-Guo,Lin, Guo-Qiang
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p. 4328 - 4331
(2014/09/30)
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- Cellulose as an efficient support for Mn(salen)Cl: Application for catalytic oxidation of sulfides to sulfoxides
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Supported Mn(salen)Cl was prepared by immobilization of a homogeneous Mn(salen)Cl complex onto cellulose and characterized by FT-IR, TGA and atomic absorption spectroscopy. This heterogeneous catalyst is able to effectively catalyze the oxidation of aromatic sulfides in good yield under mild conditions. The catalytic activity of Mn(salen)Cl and [Mn(salen)Cl-cellulose] in this reaction was investigated. The heterogeneous catalyst showed higher catalytic activity with respect to the neat Mn(salen)Cl complex. The key advantages of this process are cost effectiveness of the catalyst, reusability of the catalyst and easy work-up. This journal is
- Mohammadinezhad, Arezou,Nasseri, Mohammad Ali,Salimi, Mehri
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p. 39870 - 39874
(2014/12/11)
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- Highly efficient selective oxidation of sulfides to sulfoxides by montmorillonite-immobilized metalloporphyrins in the presence of molecular oxygen
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Highly efficient and selective oxidation of sulfides to sulfoxides with dioxygen catalyzed by cationic meso-tetrakis (1-methyl-4-pyridyl) (TM4PyP) metalloporphyrins immobilized into montmorillonite (MT) interlayer was achieved. Manganese (II) porphyrin (MnTM4PyP-MT) presented excellent activity for the oxidation of sulfides under ambient conditions. In the model oxidation, thioanisole was converted completely and the selectivity towards sulfoxide was up to 95%. This catalyst also showed high activity and selectivity for the most sulfides. The catalyst could be reused consecutively five times without significant loss of activity.
- Zhou, Xian-Tai,Ji, Hong-Bing
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- PROCESS FOR THE ASYMMETRIC OXIDATION OF ORGANIC COMPOUNDS WITH PEROXIDES IN THE PRESENCE OF A CHIRAL ACID CATALYST
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The present invention relates to a process for the asymmetric oxidation of nucleophilic organic compounds, particularly metal-free, with peroxide compounds in the presence of a chiral Bronsted acid catalyst. In one detail, the present invention relates to a process for enantioselective sulfoxidation of thiocompounds with peroxide compounds in the presence of a chiral imidodiphosphate catalyst. In another detail, the present invention relates to a process for enantioselective sulfoxidation of thiocompounds with peroxide compounds in the presence of a chiral phosphoric acid catalyst.
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Page/Page column 19-21; 24
(2013/07/25)
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- Asymmetric oxidation catalysis by a porphyrin-inspired manganese complex: Highly enantioselective sulfoxidation with a wide substrate scope
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The first genuinely promising porphyrin-inspired manganese-catalyzed asymmetric sulfoxidation method using hydrogen peroxide has been successfully developed, allowing for rapidly oxidizing (0.5-1.0 h) a wide variety of sulfides in high yields with excellent enantioselectivities (up to >99% ee).
- Dai, Wen,Li, Jun,Chen, Bo,Li, Guosong,Lv, Ying,Wang, Lianyue,Gao, Shuang
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supporting information
p. 5658 - 5661
(2013/12/04)
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- Investigation of steric and electronic effects in the copper-catalysed asymmetric oxidation of sulfides
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Steric and electronic effects in the copper-catalysed asymmetric oxidation of aryl benzyl, aryl alkyl and alkyl benzyl sulfides have been investigated. The presence of an aryl group directly attached to the sulfur is essential to afford sulfoxides with high enantioselectivities, with up to 97% ee for 2-naphthyl benzyl sulfoxide, the highest enantioselectivity achieved to date for copper-catalysed asymmetric sulfoxidation. In contrast, the benzyl substituent can be replaced by sterically comparable groups with no effect on enantioselectivity. Copper-mediated oxidation of substituted aryl benzyl sulfides display modest steric and electronic effects resulting in comparable or lower enantioselectivities to those obtained with the unsubstituted benzyl phenyl sulfide.
- O'Mahony, Graham E.,Eccles, Kevin S.,Morrison, Robin E.,Ford, Alan,Lawrence, Simon E.,Maguire, Anita R.
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supporting information
p. 10168 - 10184
(2013/11/06)
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- Sulfoxide-to-sulfilimine conversions: Use of modified Burgess-type reagents
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Sulfoxides can directly be converted into N-cyanosulfilimines using a new Burgess-type reagent. By applying this strategy with a related reagent variant, synthetically valuable NH-sulfoximines have been prepared from sulfoxides via N-protected sulfilimines. The practical three-step reaction sequence is generally high yielding and applicable to a wide range of substrates. The sulfoxide-to-sulfilimine conversion can also be performed under solvent-reduced conditions in a ball mill. Copyright
- Hendriks, Christine M. M.,Lamers, Philip,Engel, Julien,Bolm, Carsten
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supporting information
p. 3363 - 3368
(2013/12/04)
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- Oxidation reactions catalyzed by polyoxomolybdate salts
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Ionic compounds containing the polyoxomolybdate anion [Mo6O 19]2- and [(n-C4H9) 4P]+ (tetra-butylphosphonium), [(n-C4H 9)3P(n-C14H29)]+ (tributyl (tetradecyl)phosphonium), [Bmim]+ (1-butyl-3- methylimidazolium) and [Dbmim]+ (1,2-dimethyl-3-butylimidazolium) cations were prepared and characterized, including the determination of three of the solid state structures by singlecrystal X-ray diffraction. These compounds were applied as catalysts for the epoxidation of olefins with urea hydrogen peroxide (UHP) as oxidant in the ionic liquid [Bmim]PF6. Additionally, the oxidation of sulfides to sulfoxides with hydrogen peroxide (H2O2) in several solvents was investigated. The polyoxomolybdate catalysts showed a good performance for epoxidation of olefins as well as for oxidation of sulfides. Furthermore, the catalysts can be recycled several times in oxidation reactions. We present this methodology for the oxidation reaction in a simple, economically, technically, and environmentally benign manner.
- Zhang, Bo,Li, Su,Poethig, Alexander,Cokoja, Mirza,Zang, Shu-Liang,Herrmann, Wolfgang A.,Kuehn, Fritz E.
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p. 587 - 597
(2013/07/26)
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- SnO 2 nanoparticles: Preparation and evaluation of their catalytic activity in the oxidation of aldehyde derivatives to their carboxylic acid and sulfides to sulfoxide analogs
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A variety of aromatic and aliphatic aldehydes were converted to the corresponding carboxylic acid derivatives with 30% H2O2 and tert-butyl hydroperoxide as the oxidant in the presence of a catalytic amount of SnO2 nanoparticles as a precursor. These nanoparticles were also used for the efficient catalytic oxidation of sulfides to sulfoxides using 30% H2O2. The present methodology offers several advantages such as applicability to a wide range of aldehydes/sulfides, convenient work-up, mild reaction conditions as well as good yields and reasonable time of the reactions. Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.
- Dehbashi, Mohsen,Aliahmad, Mousa,Shafiee, Mohammad Reza Mohammad,Ghashang, Majid
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p. 864 - 872
(2013/08/23)
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- Kinetics and mechanism of (salen)MnIII catalyzed oxidation of methyl phenyl sulfides with sodium metaperiodate
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The kinetics of (salen)MnIII complexes-catalyzed oxidation of phenyl methyl sulfides with periodate in 90% acetonitrile-10% water (v/v) mixture at 20 °C has been studied spectrophotometrically. The oxidation follows an overall second order kine
- Chellamani, Arunachalam,Subramanian, Ramasamy
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p. 1584 - 1590
(2014/01/23)
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- A chiral porous metallosalan-organic framework containing titanium-oxo clusters for enantioselective catalytic sulfoxidation
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A chiral porous zeolite-like metal-organic framework is constructed by using mixed ligands of dipyridyl-functionalized chiral Ti(salan) and biphenyl-4,4′-dicarboxylate. The framework containing salan-bound Ti 4O6 clusters consists of both hydrophobic and amphiphilic mesocages and is shown to be an efficient and recyclable heterogeneous catalyst for the oxidation of thioethers to sulfoxides by aqueous H2O 2 (up to 82% ee), displaying markedly enhanced enantioselectivity over the homogeneous catalyst by providing a cavity confinement effect. This work highlights the potential of significantly improving enantioselectivity of homogeneous catalysts by using MOFs as support structures.
- Xuan, Weimin,Ye, Chengcheng,Zhang, Mengni,Chen, Zhijie,Cui, Yong
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p. 3154 - 3159
(2013/07/26)
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- Titanium-salan-catalyzed asymmetric sulfoxidations with H2O 2: Design of more versatile catalysts
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Titanium-salan complexes with 3,3'-diphenyl substituents in the salicylidene rings of the salan ligand are efficient sulfoxidation catalysts, capable of catalyzing the asymmetric oxidation of bulky aryl benzyl sulfides with H2O2 with good to high enantioselectivities. In this paper, substituent effects on titanium-salan-catalyzed enantioselective oxidation of sulfides to sulfoxides have been systematically investigated. Titanium-salan catalysts with halogen substituents at the 5,5'-positions (3,3'-H2dihydrogen substituted) have been found to catalyze the oxidation of both bulky aryl benzyl sulfides and small alkyl phenyl sulfides with good to high enantioselectivities. Kinetic data witness a direct attack of the sulfide to the electrophilic active oxygen species; a consistent reaction mechanism is proposed. Copyright 2013 John Wiley & Sons, Ltd. Titanium-salan complexes with halogen substituents at the 5,5'-positions are versatile catalysts for the oxidation of both bulky aryl benzyl sulfides and small alkyl phenyl sulfides, demonstrating good to high chemoselectivity (up to 92 %) and enantioselectivity (up to 93 % ee). Copyright
- Talsi, Evgenii P.,Bryliakov, Konstantin P.
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p. 239 - 244
(2013/06/04)
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- Chiral microporous Ti(salan)-based metal-organic frameworks for asymmetric sulfoxidation
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Chiral porous metal-metallosalan frameworks are constructed from an unsymmetrical chiral pyridinecarboxylate ligand derived from Ti(salan) and are shown to be heterogeneous catalysts for asymmetric oxidation of thioethers to sulfoxides.
- Zhu, Chengfeng,Chen, Xu,Yang, Zhiwei,Du, Xia,Liu, Yan,Cui, Yong
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p. 7120 - 7122
(2013/08/23)
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- Sulfinylnitriles: Sulfinyl-metal exchange-alkylation strategies
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Adding organolithiums, Grignard reagents, or zincates to sulfinylnitriles triggers a facile sulfinyl-metal exchange to afford N- or C-metalated nitriles. Sulfinyl-magnesium exchange-alkylations efficiently install quaternary and tertiary centers, even in
- Nath, Dinesh,Fleming, Fraser F.
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p. 2023 - 2029
(2013/03/14)
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- Copper-catalyzed asymmetric oxidation of sulfides
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Copper-catalyzed asymmetric sulfoxidation of aryl benzyl and aryl alkyl sulfides, using aqueous hydrogen peroxide as the oxidant, has been investigated. A relationship between the steric effects of the sulfide substituents and the enantioselectivity of th
- O'Mahony, Graham E.,Ford, Alan,Maguire, Anita R.
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experimental part
p. 3288 - 3296
(2012/05/20)
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- Metalloporphyrin-catalyzed chemoselective oxidation of sulfides with polyvinylpyrrolidone-supported hydrogen peroxide: A simple catalytic system for selective oxidation of sulfides to sulfoxides
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Room temperature oxidation of organic sulfides with polyvinylpyrrolidone- supported hydrogen peroxide (PVP-H2O2) in the presence of Mn(III) complexes of meso-tetraphenylporphyrin, Mn(TPP)X (X = OCN, SCN, OAc, Cl) and imidazole (ImH)
- Zakavi, Saeed,Abasi, Azam,Pourali, Ali Reza,Talebzadeh, Sadegh
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experimental part
p. 35 - 38
(2012/03/10)
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- Economical oxygenation of olefins and sulfides catalyzed by new molybdenum(VI) tridentate schiff base complexes: Synthesis and crystal structure
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New cis-dioxomolybdenum(VI) complexes (MoO2YxCH 3OH) were synthesized using MoO2(acac)2 and 2[(1-hydroxy-2-methylpropane-2-ylimino)methyl]phenol derivatives as tridentate ONO donor Schiff base ligands (H2Yx). MoY1 was crystallized in orthorhombic space group Pbca. The epoxidation of olefins using tert-butyl hydroperoxide and oxidation of sulfides to the sulfoxides by hydrogen peroxide were efficiently enhanced by the catalytic activity of title Mo VI complexes with excellent selectivity. The high efficiency and relative stability of the catalysts was observed by turnover number and UV/Vis investigations. The electron-rich and bulky ligands promoted the effectiveness of the catalysts. Copyright
- Rezaeifard, Abdolreza,Jafarpour, Maasoumeh,Raissi, Heidar,Alipour, Mahboubeh,Stoeckli-Evans, Helen
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experimental part
p. 1023 - 1030
(2012/08/07)
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- Activation of H2O2 by chiral confined Bronsted acids: A highly enantioselective catalytic sulfoxidation
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Confined chiral Bronsted acids are shown to catalyze asymmetric oxidations of sulfides to sulfoxides with hydrogen peroxide. The wide generality and high enantioselectivity of the developed method compare even to the best metal-based systems and suggest utility in other asymmetric oxidations.
- Liao, Saihu,Coric, Ilija,Wang, Qinggang,List, Benjamin
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supporting information; experimental part
p. 10765 - 10768
(2012/08/28)
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- Asymmetric counteranion-directed iron catalysis: A highly enantioselective sulfoxidation
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A highly active and enantioselective ion-pair sulfoxidation catalyst, consisting of an achiral iron(III)-salen cation and a chiral phosphate counteranion, mediates the oxidization of various sulfides with high yields and enantioselectivities. The enantioselectivities observed, especially for electron-poor substrates, represent the best results so far in manganese and iron-salen systems. This work represents the first application of our concept of asymmetric counteranion-directed catalysis (ACDC) to iron catalysis. Copyright
- Liao, Saihu,List, Benjamin
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supporting information
p. 2363 - 2367
(2012/10/30)
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- Desymmetrization of prochiral diaryl sulfoxides by an asymmetric sulfoxide-magnesium exchange
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The first desymmetrizations of prochiral diaryl sulfoxides 1 by an asymmetric sulfoxide-magnesium exchange reaction are reported. The respective substrate (1), iPr2Mg, and the dilithium salt of (S)-BINOL (which was prepared in situ) provided (S)-configured aryl isopropyl sulfoxides 2 in up to 91 % yield and with up to 91 % ee. (S)-BINOL was re-isolable in 98 % yield. Copyright
- Hampel, Thomas,Ruppenthal, Simon,Saelinger, Daniel,Brueckner, Reinhard
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p. 3136 - 3140
(2012/05/20)
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- Application of a novel 1,3-diol with a benzyl backbone as chiral ligand for asymmetric oxidation of sulfides to sulfoxides
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A chiral 1,3-diol with a benzyl backbone has been used for the asymmetric oxidation of sulfides to sulfoxides. Moderate to good yields and enantioselectivity (upto 87% ee) have been observed.
- Gogoi, Paramartha,Kotipalli, Trimurthulu,Indukuri, Kiran,Bondalapati, Somasekhar,Saha, Pipas,Saikia, Anil K.
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supporting information; experimental part
p. 2726 - 2729
(2012/07/17)
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