- Flow Electrosynthesis of Sulfoxides, Sulfones, and Sulfoximines without Supporting Electrolytes
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An efficient electrochemical flow process for the selective oxidation of sulfides to sulfoxides and sulfones and of sulfoxides toN-cyanosulfoximines has been developed. In total, 69 examples of sulfoxides, sulfones, andN-cyanosulfoximines have been synthesized in good to excellent yields and with high current efficiencies. The synthesis was assisted and facilitated through a supporting electrolyte-free, fully automated electrochemical protocol that highlights the advantages of flow electrolysis.
- Amri, Nasser,Wirth, Thomas
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p. 15961 - 15972
(2021/07/20)
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- One-Pot Synthesis of N-Iodo Sulfoximines from Sulfides
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This is the first report on the synthesis and characterization of N-iodo sulfoximines. The synthesis was designed as a room temperature one-pot cascade reaction from readily available sulfides as starting compounds, converted into sulfoximines by reaction with ammonium carbonate and (diacetoxyiodo)benzene, followed by iodination with N-iodosuccinimide or iodine in situ, in up to 90% isolated yields, also at a multigram scale. Iodination of aryls with N-iodo sulfoximines, oxidation, and conversion to N-SCF3 congeners have been demonstrated.
- Zupanc, An?e,Jereb, Marjan
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p. 5991 - 6000
(2021/05/05)
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- Blue light-promoted radical sulfoximido-chalcogenization of aliphatic and aromatic alkenes
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A transition metal-free synthesis ofN-(arylthio/seleno)ethyl sulfoxidminesviablue light-promoted radical sulfoximido-chalcogenization of aliphatic and aromatic alkenes was developed. The sulfoximidation process demonstrated high chemoselectivity and allowed a broad substrate scope, completing the sulfoximido-chalcogenization of alkenes in good yields.
- Chen, Hongyi,Chen, Li,He, Ze,Zeng, Qingle
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supporting information
p. 2624 - 2627
(2021/04/21)
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- Sulfoximines-assisted Rh(III)-catalyzed C-H activation and intramolecular annulation for the synthesis of fused isochromeno-1,2-benzothiazines scaffolds under room temperature
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Amild and facile Cp?Rh(III)-catalyzed C-Hactivation and intramolecular cascade annulation protocol has been proposed for the furnishing of highly fused isochromeno-1,2-benzothiazines scaffolds using S-phenylsulfoximides and 4-diazoisochroman-3-imine as substrates under room temperature. This method features diverse substituents and functional groups tolerance and relatively mild reaction conditions with moderate to excellent yields. Additionally, retentive configuration of sulfoximides in the conversion has been verified.
- Han, Xu,Li, Chunpu,Li, Jian,Liu, Hong,Wang, Bao
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- Palladium-Catalyzed Electrochemical C-H Bromination Using NH4Br as the Brominating Reagent
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The palladium-catalyzed electrochemical C-H bromination of benzamide derivatives under divided cells is developed, in which NH4Br serves as a brominating reagent and electrolyte. The protocol avoids the use of chemical oxidants and provides an alternative method for the synthesis of aryl bromides.
- Yang, Qi-Liang,Wang, Xiang-Yang,Wang, Tong-Lin,Yang, Xiang,Liu, Dong,Tong, Xiaofeng,Wu, Xin-Yan,Mei, Tian-Sheng
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p. 2645 - 2649
(2019/04/17)
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- Ru (II)-Catalyzed Coupling-Cyclization of Sulfoximines with alpha-Carbonyl Sulfoxonium Ylides as an Approach to 1,2-Benzothiazines
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A Ru(II)-catalyzed approach for the rapid assembly of 1,2-benzothiazines has been developed to enable the coupling-cyclization of aryl Csp2?H bonds with α-carbonyl sulfoxonium ylides via Csp2?H activation process. The present method could be further applied to the construction of the 4-substituted 1,2-benzothiazine skeletons. (Figure presented.).
- Xie, Haisheng,Lan, Jianyong,Gui, Jiao,Chen, Fengjuan,Jiang, Huangfeng,Zeng, Wei
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p. 3534 - 3543
(2018/08/06)
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- Iron(II)-Catalyzed Direct Synthesis of NH Sulfoximines from Sulfoxides
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Free NH-sulfoximines were directly prepared from sulfoxides through iron catalysis by applying a readily available, shelf-stable hydroxylamine triflic acid salt. No additional oxidant is needed, and the substrate scope is broad, including a range of heter
- Yu, Hao,Li, Zhen,Bolm, Carsten
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supporting information
p. 324 - 327
(2017/12/15)
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- A Convenient, Mild, and Green Synthesis of NH-Sulfoximines in Flow Reactors
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NH-sulfoximines are emerging as useful and important targets in drug discovery and synthetic organic chemistry. We report herein the development of an efficient, convenient, and sustainable continuous-flow strategy, for the direct, straightforward preparation of NH-sulfoximines by using sulfides or sulfoxides as suitable starting material. The flow process uses PhI(OAc)2 as the oxidant and aqueous solutions of ammonia as the N source. The scope of the reaction has been demonstrated by using several substituted sulfides and sulfoxides including enantioenriched and biologically relevant starting materials. The flow strategy was found to be more convenient with respect to conventional batch processing.
- Degennaro, Leonardo,Tota, Arianna,De Angelis, Sonia,Andresini, Michael,Cardellicchio, Cosimo,Capozzi, Maria Annunziata,Romanazzi, Giuseppe,Luisi, Renzo
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supporting information
p. 6486 - 6490
(2017/09/13)
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- Mechanistic investigation of the NH-sulfoximination of sulfide. Evidence for λ6-sulfanenitrile intermediates
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We report a new procedure for the preparation of NH-sulfoximines from sulfides using PIDA as an oxidant and ammonium carbamate as the ammonia source. Excellent yields were obtained with a wide range of sulfides. The formation of acetoxy- and methoxy-λsup
- Lohier, Jean-Fran?ois,Glachet, Thomas,Marzag, Hamid,Gaumont, Annie-Claude,Reboul, Vincent
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supporting information
p. 2064 - 2067
(2017/02/15)
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- Eaton's reagent-mediated metal-free and efficient synthesis of NH-sulfoximines
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NH-sulfoximines can be prepared efficiently from corresponding sulfoxides in the presence of sodium azide and Eaton's reagent. This metal-free and efficient methodology is applicable to a wide variety of functionalized sulfoxides to afford NH-sulfoximines in good to excellent yields with shorter reaction time than previously reported methods.
- Wang, Jianping,Zhang, Jian,Miao, Kun,Yun, Hongying,Shen, Hong C.,Zhao, Weili,Liang, Chungen
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supporting information
p. 333 - 337
(2017/01/03)
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- Rhodium-catalyzed direct synthesis of unprotected NH-sulfoximines from sulfoxides
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A novel rhodium-catalyzed imination of sulfoxides using O-(2,4-dinitrophenyl)hydroxylamine is developed under mild conditions with good functional group tolerance. This method provides an efficient access to free NH-sulfoximines, an important structural u
- Miao, Jinmin,Richards, Nigel G. J.,Ge, Haibo
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supporting information
p. 9687 - 9689
(2014/08/18)
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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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p. 3363 - 3368
(2013/12/04)
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- Pd(II)-catalyzed primary-C(sp3)-H acyloxylation at room temperature
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With the aid of a novel S-methyl-S-2-pyridyl-sulfoximine (MPyS) directing group (DG), the unactivated primary β-C(sp3)-H bond of MPyS-N-amides oxidizes at room temperature. The catalytic conditions are applicable to the diacetoxylation of primary β,β′-C(sp 3)-H bonds, and the carboxylic acid solvent is pivotal in the formation of the C-O bond. The MPyS-DG cleaves from the oxidation products and is recovered. This method provides convenient access to α,α′- disubstituted-β-hydroxycarboxylic acids.
- Rit, Raja K.,Yadav, M. Ramu,Sahoo, Akhila K.
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p. 3724 - 3727
(2012/08/28)
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- Iodinane- and metal-free synthesis of N-cyano sulfilimines: Novel and easy access of NH-sulfoximines
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The synthesis of W-cyanosulfilimines can readily be achieved by reaction of the corresponding sulfides with cyanogen amine in the presence of a base and NBS or l2 as halogenating agents. Oxidation followed by C-N bond cleavage affords synthetically useful WH-free sulfoximines.
- Mancheno, Olga Garcia,Bistri, Olivia,Bolm, Carsten
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p. 3809 - 3811
(2008/02/12)
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- Comparative study of metal-catalyzed iminations of sulfoxides and sulfides
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A comparative study of the imination of sulfur compounds with various metal catalysts in combination with isolated or in situ generated iminoiodinanes (PhI=NR) as nitrogen sources is presented. The influence of the metal catalyst towards the imination of a variety of substituted sulfoxides has been evaluated. Moreover, the effect of the different oxidation states of sulfur on the reactivity and selectivity of the nitrogen transfer redox process in the formation of sulfilimines and sulfoximines was studied. Depending on both the specific metal catalyst as well as the employed nitrene precursor, the sulfide/sulfoxide imination ratio varied in transformations of thianthrene-5-oxide and substituted para-thio phenylsulfoxides.
- Mancheno, Olga Garcia,Bolm, Carsten
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p. 6674 - 6681
(2008/03/15)
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- Syntheses and Some Properties of Sulfoxides, Sulfilimines, Aminosulfonium Salts and Sulfoximines Containing Pyridine Nuclei
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Several 2-pyridyl sulfides (1) (e.g., methyl (1a), ethyl (1b), isopropyl (1c), benzyl (1d), 1-phenylethyl (1e), l-menthyl (1f) 2-pyridyl sulfides); and bis(2-pyridylthio)methane (1g), and methyl 2-(N-oxy-pyridyl) sulfide (1h) were prepared by the usual method.Sulfoxides (2) were prepared by oxidation of the corresponding sulfides with m-chloroperbenzoic acid in good yields.A few sulfoxides were found to work as phase-transfer catalysts for some typical nucleophilic reactions in nonpolar solvents such as benzene, and in two-phase systems such as benzene-water.S-2-Pyridyl-N-(p-toluenesulfonyl) sulfinilimines (3) were prepared upon treatment of sulfides with Chloramine-T.Hydrolysis of N-(p-toluenesulfonyl)-2-pyridyl-o-tolylsulfilimine (3i) with conc. sulfuric acid gave the corresponding free sulfilimine in a moderate yield.S-2-Pyridyl sulfoximines (4) were not obtained by the general method from the sulfoxides and hydrazoic acid.Alkyl-2-pyridyl sulfoximines, however, were obtained by oxidation of the free sulfilimines derived from the corresponding aminosulfonium salts (5) prepared by reaction of the sulfides with mesitylene-sulfonylhydroxylamine (MSH).These free sulfilimines and sulfoximines thus prepared were found to give adducts with a few copper salts.
- Furukawa, Naomichi,Takahashi, Fujio,Tsutomu, Kawai,Kishimoto, Keiko,Ogawa, Satoshi,Oae, Shigeru
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p. 167 - 180
(2007/10/02)
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- REDUCTIVE DEIMINATION OF SULFOXIMIDES AND SULFIMIDES WITH P-TOLUENESULFONYL NITRITE AND T-BUTYL THIONITRATE
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Reduction of sulfimides and sulfoximides with p-toluenesulfonyl nitrite, a new nitrosating agent, gave nearly quantitatively the corresponding deimination products, sulfides and sulfoxides, respectively.In the reaction of dialkyl and aryl alkyl sulfoximides with t-butyl thionitrate, N-t-butylthiosulfoximides were obtained besides the usual deimination products, although diaryl sulfoximides were readily deiminated to the corresponding sulfoxides in good yields in the same treatment. t-Butyl thionitrsate was also found to deiminate diphenyl sulfimide to give diphenyl sulfide in good yield.Sulfoximides reacted sluggishly with t-butyl thionitrite, however, eventually affording a small amount of sulfoxides.
- Oae, Shigeru,Iida, Kazuyuki,Takata, Toshikazu
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p. 103 - 114
(2007/10/02)
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- SYNTHESES AND CHEMICAL PROPERTIES OF SULFOXIDES, SULFILIMINES AND SULFOXIMINES CONTAINING PYRIDINE NUCLEI
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Several 2-pyridyl sulfides, sulfoxides and N-(p-toluenesulfonyl)-sulfilimines were prepared by the usual methods.Hydrolysis of N-(p-toluenesulfonyl)-2-pyridyl-o-tolylsulfilimine with conc. sulfuric acid gave the corresponding N-unsubstituted (free) sulfilimine in a moderate yield.Sulfoximines were obtained by oxidation of the corresponding free sulfilimines derived from the aminosulfonium salts.These free sulfilimines and sulfoximines thus prepared were found to give adducts with few Cu-salts.Methyl 2-pyridyl sulfoxide was found to be a good phase transfer catalyst for some typical nucleophilic reactions.
- Furukawa, Naomichi,Takahashi, Fujio,Kishimoto, Keiko,Morito, Hiroyuki,Oae, Shigeru
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p. 1273 - 1278
(2007/10/02)
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