- Rhodium(iii)-catalyzed cascade C-H functionalization/annulation of sulfoximines with iodonium ylides for the synthesis of cyclohexanone-1,2-benzothiazines
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A highly efficient Rh(iii)-catalyzed cascade C-H activation/annulation of sulfoximines with iodonium ylides under metal-oxidant-free conditions has been reported. The fused cyclohexanone-1,2-benzothiazine scaffold is readily achieved with a one-pot proces
- Chen, Lu,Hao, Liqiang,Ji, Yafei,Wang, Yangyang,Wang, Zhichao,Wu, Gaorong,Xu, Xiaobo
-
supporting information
p. 887 - 894
(2022/02/03)
-
- 2-Sulfoximidoyl acetic acids from multicomponent petasis reactions and their use as building blocks in syntheses of sulfoximine benzodiazepine analogues
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Upon application of a multicomponent Petasis reaction, a broad range of NH-sulfoximines and boronic acids react with glyoxalic acid to afford the corresponding 2-substituted acetic acids with N-bound sulfoximidoyl groups. The protocol features excellent y
- Hommelsheim, Renè,Nú?ez Ponce, Heliana Michaela,Truong, Khai-Nghi,Rissanen, Kari,Bolm, Carsten
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p. 3415 - 3420
(2021/05/04)
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- Electrochemical Oxidative Syntheses of NH-Sulfoximines, NH-Sulfonimidamides and Dibenzothiazines via Anodically Generated Hypervalent Iodine Intermediates
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Herein, we report a general method for the synthesis of NH-sulfoximines and NH-sulfonimidamides through direct electrochemical oxidative catalysis involving an iodoarene(I)/iodoarene(III) redox couple. In addition, dibenzothiazines can be synthesized from [1,1′-biaryl]-2-sulfides under standard conditions. Notably, only a catalytic amount of iodoarene is required for the generation in situ of an active hypervalent iodine catalyst, which avoids the need for an excess of a hypervalent iodine reagent relative to conventional approaches. Moreover, this protocol features broad substrate scope and wide functional group tolerance, delivering the target compounds with good-to-excellent yields even for a scale of more than 10 g.
- Kong, Xianqiang,Lin, Long,Chen, Xiaohui,Chen, Yiyi,Wang, Wei,Xu, Bo
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p. 3277 - 3282
(2021/07/26)
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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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- Sulfoximines Assisted Rh(III)-Catalyzed C-H Activation/Annulation Cascade to Synthesize Highly Fused Indeno-1,2-benzothiazines
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A facile access to highly fused tetracyclic indeno-1,2-benzothiazines has been established via a Rh(III)-catalyzed C-H bond activation and intramolecular annulation cascade between sulfoximides and all-carbon diazo indandiones. This strategy is characterized by the fact that the diazo coupling partners do not require preactivation, along with its high efficiency, broad substrate generality, and facile transformation. Particularly, the highly conjugated tetracyclic products demonstrate good optical properties and can easily enter cells to emit bright fluorescence for live cell imaging.
- Li, Jian,Li, Hui,Fang, Daqing,Liu, Lingjun,Han, Xu,Sun, Jina,Li, Chunpu,Zhou, Yu,Ye, Deju,Liu, Hong
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p. 15217 - 15227
(2021/10/25)
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- Synthesis of NH-Sulfoximines by Using Recyclable Hypervalent Iodine(III) Reagents under Aqueous Micellar Conditions
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The synthesis of NH-sulfoximines from sulfides has been first developed under mild conditions in an aqueous solution with surfactant TPGS-750-M as the catalyst at room temperature. In this newly developed process, a simple and convenient recycling strategy to regenerate the indispensable hypervalent iodine(III) is used. The resulting 1,2,3-trifluoro-5-iodobezene can be recovered almost quantitively from the mixture by liquid–liquid extraction and then oxidized to give the corresponding iodine(III) species. This optimized procedure is compatible with a broad range of functional groups and can be easily performed on a gram scale, providing a green protocol for the synthesis of sulfoximines.
- Zhang, Guocai,Tan, Hongsheng,Chen, Weichun,Shen, Hong C.,Lu, Yue,Zheng, Changwu,Xu, Hongxi
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p. 922 - 928
(2020/02/20)
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- Palladium-Catalyzed Oxidative Annulation of Sulfoximines and Arynes by C-H Functionalization as an Approach to Dibenzothiazines
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This work reports a novel and efficient palladium-catalyzed synthesis of tricyclic dibenzothiazines using easily prepared aryl sulfoximines and aryne precursors via C-H functionalization and cyclization. A mechanistic investigation indicated that the C-H bond cleavage at the position ortho to the sulfoximine group is the rate-determining step.
- Li, Jing,Li, Shan,Liu, Liansheng,Wang, Rong,Wei, Junfa,Yang, Yihui
-
supporting information
p. 7470 - 7474
(2020/10/09)
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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
-
-
- Enantioselective Synthesis of Chiral-at-Sulfur 1,2-Benzothiazines by CpxRhIII-Catalyzed C?H Functionalization of Sulfoximines
-
Sulfoximines with stereogenic sulfur atoms are attractive structural motifs in drug discovery. A direct catalytic enantioselective method for the synthesis of sulfur-chiral 1,2-benzothiazines from readily accessible diaryl sulfoximines is presented. Rhodium(III) complexes equipped with chiral cyclopentadienyl ligands and paired with suitable carboxylic acid additives engage in an enantiodetermining C?H activation directed by the sulfoximine group. Subsequent trapping of the rhodacycle with a broad range of diazoketones gives access to S-chiral 1,2-benzothiazines with synthetically highly attractive substitution patterns in good yields and enantioselectivities.
- Sun, Yang,Cramer, Nicolai
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p. 15539 - 15543
(2018/11/02)
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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)
-
- Synthesis of NH-sulfoximines from sulfides by chemoselective one-pot N- and O-transfers
-
Direct synthesis of NH-sulfoximines from sulfides has been achieved through O and NH transfer in the same reaction, occurring with complete selectivity. The reaction is mediated by bisacetoxyiodobenzene under simple conditions and employs inexpensive N-so
- Tota, Arianna,Zenzola, Marina,Chawner, Stephen J.,John-Campbell, Sahra St,Carlucci, Claudia,Romanazzi, Giuseppe,Degennaro, Leonardo,Bull, James A.,Luisi, Renzo
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supporting information
p. 348 - 351
(2017/01/03)
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- Straightforward Strategies for the Preparation of NH-Sulfox-imines: A Serendipitous Story
-
Sulfoximines are emerging as valuable new isosteres for use in medicinal chemistry, with the potential to modulate physicochemical properties. Recent developments in synthetic strategies have made the unprotected 'free' NH-sulfoximine group more readily available, facilitating further study. This account reviews approaches to NH-sulfoximines, with a focus on our contribution to the field. Starting from the development of catalytic strategies involving transition metals, more sustainable metal-free processes have been discovered. In particular, the use of hypervalent iodine reagents to mediate NH-transfer to sulfoxides is described, along with an assessment of the substrate scope. Furthermore, a one-pot strategy to convert sulfides directly into NH-sulfoximines is discussed, with N- and O-transfer occurring under the reaction conditions. Mechanistic evidence for the new procedures is included as well as relevant synthetic applications that further exemplify the potential of these approaches. 1 Introduction 2 Strategies to Form NH-Sulfoximines Involving Transition-Metal Catalysts 3 Metal-Free Strategies to Prepare NH-Sulfoximines 4 Mechanistic Evidence for the Direct Synthesis of NH-Sulfoximines from Sulfoxides and Sulfides 5 Further Applications 6 Conclusion.
- Bull, James A.,Degennaro, Leonardo,Luisi, Renzo
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p. 2525 - 2538
(2017/11/28)
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- Mechanistic investigation of the NH-sulfoximination of sulfide. Evidence for λ6-sulfanenitrile intermediates
-
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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- Method for synthesizing sulfoximine compounds from thioether
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The invention discloses a synthetic method for synthesizing sulfoximine compounds from thioether in one step and application thereof. The synthetic method disclosed by the invention comprises the step of mixing the thioether, an ammonia source and an organic solvent together for carrying out an oxidizing reaction in the presence of an oxidizing agent, thereby obtaining the corresponding sulfoximine compounds. According to the invention, one-step synthesis of the sulfoximine compounds from the thioether is realized for the first time. In recent years, the sulfoximine structure is introduced into the existing drug molecules or high-activity compound molecules, and many high-activity molecules at the clinical stage and listed drug molecules appear. According to the method disclosed by the invention, the drug molecules containing the sulfoximine structure are produced, and the industrial cost can be greatly reduced; and moreover, the synthetic method provided by the invention has the advantages of being high in yield, readily available in raw materials, simple in conditions, simple in reaction equipment, easy in industrialized production, and the like. The structural formula is as shown in the specification.
- -
-
Paragraph 0035; 0036
(2017/08/28)
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- Metal-Free, Phosphonium Salt-Mediated Sulfoximination of Azine N-Oxides: Approach for the Synthesis of N-Azine Sulfoximines
-
Herein, we report a simple and metal-free method for the synthesis of N-azine sulfoximines by the nucleophilic substitution of azine N-oxides with NH-sulfoximines. The present method works at room temperature with wide functional group compatibility and gives several unprecedented N-azine sulfoximines. The reaction conditions were also found suitable with enantiopure substrates and furnished products without any racemization. It also finds an application in the sulfoximination of azine-based functional molecules such as 2,2′-bipyridine, 1,10-phenanthroline, and quinine.
- Aithagani, Sravan Kumar,Kumar, Mukesh,Yadav, Mahipal,Vishwakarma, Ram A.,Singh, Parvinder Pal
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p. 5886 - 5894
(2016/07/23)
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- Iron-Catalyzed Acylative Dealkylation of N-Alkylsulfoximines
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As a result of our recent investigations into the N-functionalization of sulfoximines, an iron-catalyzed dealkylative acylation of N-alkylsulfoximines has been developed. This process involves a Polonovski-type dealkylation of an N-alkylated sulfoximine to afford a reactive intermediate that is trapped in the presence of a suitable aldehyde or anhydride to afford N-acyl- and N-aroylsulfoximine derivatives in one pot. Subsequent cleavage of the acyl or aroyl group under acidic conditions generates a synthetically valuable NH-sulfoximine. The dealkylation of N-alkylsulfoximines has been developed utilizing TBHP as oxidant and a catalytic amount of iron chloride to furnish a range of N-acyl- and N-aroylsulfoximines. This method facilitates the use of N-alkyl protecting groups that provide very stable N-protected sulfoximine derivatives that can be readily modified at sites other than the nitrogen atom.
- Lamers, Philip,Priebbenow, Daniel L.,Bolm, Carsten
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p. 5594 - 5602
(2015/09/01)
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- Metal-Free Approach for the Synthesis of N-Aryl Sulfoximines via Aryne Intermediate
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A metal-free and operationally simple N-arylation of NH-sulfoximines with aryne precursors is reported. Transition metal-free reaction conditions and shorter reaction times are the highlights of the present method. The mild optimized condition was also found to be suitable with enantiopure substrates.
- Aithagani, Sravan Kumar,Dara, Saidulu,Munagala, Gurunadham,Aruri, Hariprasad,Yadav, Mahipal,Sharma, Shweta,Vishwakarma, Ram A.,Singh, Parvinder Pal
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p. 5547 - 5549
(2015/12/01)
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- N-alkylations of NH-sulfoximines and NH-sulfondiimines with alkyl halides mediated by potassium hydroxide in dimethyl sulfoxide
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A general method for the N-alkylation of NH-sulfoximines and NH-sulfondiimines has been developed, employing alkyl bromides with KOH in DMSO at room temperature. A variety of previously inaccessible N-alkylated sulfoximines and sulfondiimines was prepared in good to excellent yields (up to 97%). As an application, the conditions were used to access the biologically active Suloxifen.
- Hendriks, Christine M. M.,Bohmann, Rebekka A.,Bohlem, Marina,Bolm, Carsten
-
supporting information
p. 1847 - 1852
(2014/06/09)
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- Sulfoximines: A reusable directing group for chemo-and regioselective ortho C-H oxidation of arenes
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Sulfoximines direct: A new protocol for the chemo-and regioselective ortho C-H acetoxylation of arenes in N-benzoylated sulfoximines is reported. The sulfoximine directing group is easily detached from the C-H oxidation product through acid-promoted hydrolysis, isolated, and reused (see scheme). The meta-substituted phenols are synthesized following this strategy and the stereointegrity of the sulfoximine is preserved in this transformation. C(sp3)-H acetoxylation of the methyl group is also demonstrated.
- Yadav, M. Ramu,Rit, Raja K.,Sahoo, Akhila K.
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p. 5541 - 5545
(2012/06/01)
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- Convenient preparation of N-monosubstituted S,S-diarylsulfodiimides using fluoro-λ6-sulfanenitriles
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The reaction of fluorodiphenyl-λ6-sulfanenitrile with primary alkyl- or aryl-amines in the presence of acid catalysts or tertiary amines gave N-monosubstituted S,S-diphenylsulfodiimides effectively.
- Yoshimura, Toshiaki,Ishikawa, Hiroki,Fujie, Tetsuo,Takata, Eiichi,Miyatake, Ryuta,Kita, Hiroshi,Tsukurimichi, Eiichi
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experimental part
p. 1835 - 1840
(2009/04/04)
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- NOVEL SULPHOXIMINE-SUBSTITUTED QUINAZOLINE AND QUINAZOLINE DERIVATIVES AS KINASE INHIBITORS
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The present invention relates to a quinoline or quinazoline derivative having the general formula (A): in which R3, R4, W, Y and Q are indicated in the description and the claims, the use of the compounds of the general formula (A) f
- -
-
Page/Page column 34
(2009/01/20)
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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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- Application of alkoxy-λ6-sulfanenitriles as strong alkylating reagents
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Alkoxy-λ6-sulfanenitriles were found to be versatile alkylating reagents toward various nucleophiles bearing at least one proton such as methanol, phenol, thiophenols, carboxylic acids, ptoluenesulfonic acid, hydrochloric acid, and primary and secondary amines. Reactivity of the alkoxy group of the λ6-sulfanenitriles showed an opposite trend to the usual SN2 character, i.e. Me (la), Pr (1b), and Bu (1d) ? i-Pr (1c). In the presence of p-TsOH, alkyl tosylates were predominantly formed instead of the alkylation products of nucleophiles. In addition, even a sterically hindered substrate, neopentyloxy-λ6-sulfanenitrile, was found to undergo an SN2 reaction toward thiophenol without any rearrangement product to give neopentyl phenyl sulfide in good yield.
- Hao, Wei,Fujii, Takayoshi,Dong, Tiaoling,Wakai, Youko,Yoshimura, Toshiaki
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p. 193 - 198
(2007/10/03)
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- Rhodium-catalyzed imination of sulfoxides and sulfides: Efficient preparation of N-unsubstituted sulfoximines and sulfilimines
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The Rh(II)-catalyzed imination of sulfoxides and sulfides using [Rh 2(OAc)4] as a catalyst and trifluoroacetamide or sulfonylamides in combination with iodobenzene diacetate and magnesium oxide affords sulfoximines and sulfilimines, respectively, in a stereospecific manner.
- Okamura, Hiroaki,Bolm, Carsten
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p. 1305 - 1307
(2007/10/03)
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- Electrochemical Imination of Sulfoxides Using N-Aminophthalimide
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(Equation Presented) A novel electrochemical sulfoxide imination process is described. Our approach starts with a highly selective nitrene transfer from N-aminophthalimide to a variety of sulfoxides. This oxidative treatment is followed by reductive N-N bond cleavage under the controlled current conditions, which leads to a range of parent NH sulfoximines. In addition to solving the challenging problem of removing the N-phthalimido group, the overall process avoids the use of toxic oxidants and metal additives.
- Siu, Tung,Yudin, Andrei K.
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p. 1839 - 1842
(2007/10/03)
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- Kinetic investigation on the hydrolysis of aryl(fluoro)(phenyl)-λ6-sulfanenitriles
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A kinetic investigation on the hydrolysis of aryl(fluoro)(phenyl)-λ6-sulfanenitriles was carried out in some aqueous and mixed aqueous-organic solutions. The pH-rate profiles showed that the hydrolysis consists of pH-independent, acidcatalyzed
- Dong,Fujii,Murotani,Dai,Ono,Morita,Shimasaki,Yoshimura
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p. 945 - 954
(2007/10/03)
-
- Study of the mechanism for the hydrolysis of alkoxy(aryl)(phenyl)-λ6- sulfanenitriles, ArPhS(OR)(?N)
-
The hydrolysis of alkoxy(aryl)(phenyl)-λ6-sulfanenitriles in several buffer solutions was found to follow a good pseudo-first-order kinetic equation, giving the corresponding sulfoximides and alcohols (for the case of the hydrolysis of neopentyloxy-λ6-sulfanenitrile, giving a rearranged product, 2-methyl-2-butanol). The dependence of the rate of hydrolysis on the structure of the alkyl group showed the opposite trend to the usual S(N)2 character, i.e. Me +] at pH more than 6.08, and trends to saturate at low pH. According to these kinetic results, a two-step reaction mechanism was proposed which involves a pre-equilibrium protonation on the nitrogen atom of the alkoxy-λ6- sulfanenitriles, followed by a rate-determining C-O bond cleavage via an S(N)2 or S(N)1 mechanism on the alkyl carbon atom depending on the structure of the alkyl group. From a double-reciprocal plot of 1/k(obs) vs. 1/[H+], the pK(a) value and the rate constant of the second reaction of neopentyloxy(diphenyl)-λ6-sulfanenitrile were estimated to be 5.02 and 7.02x10-3 s-1, respectively. The substituent effects on the phenyl group of neopentyloxy(diphenyl)-λ6-sulfanenitrile afforded a large negative p- value (-1.88) for pK(a) and positive one (+1.66) for the second reaction at 25.2 °C. The small negative p-values observed at pH 6.27 for diphenyl(propoxy)-λ6-sulfanenitrile (-0.42) and neopentyloxy(diphenyl)- λ6-sulfanenitrile (-0.26) were found to be the results of a cancellation of those for the opposite trend of the reactions of the pre-equilibrium and the second step. The activation parameters for both the pre-equilibrium and the subsequent reactions were also estimated based on the parameters for the hydrolysis of neopentyloxy(diphenyl)-λ6-sulfanenitrile at pH 6.22 and 2.99. The buffer effect is due to a nucleophilic attack of the buffer base to the alkyl carbon atom of the protonated alkoxy-λ6-sulfanenitriles. The sulfoximide moiety in the protonated λ6-sulfanenitrile is revealed to be a very good leaving group.
- Yoshimura, Toshiaki,Dong, Tiaoling,Fujii, Takayoshi,Ohkubo, Masanori,Sakuta, Mikiko,Wakai, Youko,Ono, Shin,Morita, Hiroyuki,Shimasaki, Choichiro
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p. 957 - 965
(2007/10/03)
-
- Synthesis, Structure, and Thermolysis Mechanism of S-Alkoxythiazynes
-
S-Alkoxy-S,S-diarylthiazynes were prepared by two methods: the alkaline hydrolysis of S,S-diaryl-N-halosulfilimines in aqueous alcohols and the reaction of S,S-diaryl-S-fluorothiazynes with sodium alkoxides. The structure of S,S-diphenyl-S-propoxythiazyne was determined by an X-ray crystallographic analysis, which showed a short SN bond length of 1.441(3) A. The thermolysis of S-alkoxythiazynes gave elimination products, which were identified as the corresponding carbonyl compounds and N-unsubstituted S,S-diarylsulfilimines. Kinetic experiments for the thermolysis of the S-alkoxy-S,S-diarylthiazynes were carried out. The first-order kinetic behavior, a large kinetic isotope effect (kHkD = 6.1 ) using S,S-diphenyl-S-[1,1-2H2]propoxythiazyne, a negative activation entropy (ΔS? = -30 J K-1mol-1), and a negative Hammett ρ-value (ρ= -0.35) on the phenyl group were obtained, suggesting that the reaction proceeds via a concerted five-membered cyclic transition state. A deviation from the ideal concerted transition state is discussed in comparison with that for sulfoxides.
- Yoshimura, Toshiaki,Ohkubo, Masanori,Fujii, Takayoshi,Kita, Hiroshi,Wakai, Youko,Ono, Shin,Morita, Hiroyuki,Shimasaki, Choichiro,Horn, Ernst
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p. 1629 - 1637
(2007/10/03)
-
- First Preparation and Reactions of S,S-Diaryl-S-fluorothiazynes, Ar2SF(N)
-
S,S-Diaryl-S-fluorothiazynes, Ar2SF(N), were prepared by the reaction of S,S-diaryl-N-bromosulfilimines with tetrabutylammonium fluoride.The thiazyne structure was assigned by the spectral data, physical properties, and is consistent with reactions wit
- Yoshimura, Toshiaki,Kita, Hiroshi,Takeuchi, Kyu,Takata, Eiichi,Hasegawa, Kiyoshi,et al.
-
p. 1433 - 1436
(2007/10/02)
-
- Preparation and Reactivities of S,S-Diaryl-S-aminothiazynes, Ar2S(NR2)(N)
-
Reaction of S,S-diaryl-S-fluorothiazynes with cyclic secondary amines gave novel thiazynes, the corresponding S-aminothiazynes in good yields.Spectroscopic studies, measurement of pKa values, pyrolysis and alkylation reactions of the aminothiazynes were carried out.
- Yoshimura, Toshiaki,Takata, Eiichi,Miyake, Takahiro,Shimasaki, Choichiro,Hasegawa, Kiyoshi,Tsukurimichi, Eiichi
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p. 2213 - 2216
(2007/10/02)
-
- Mechanism of Reaction of S,S-Diphenyl-S-methoxythiazyne with Thiole
-
The reaction of S,S-diphenyl-S-methoxythiazyne with various thiols gave methyl sulfides.Kinetic investigations support a mechanism involving an initial protonation of the thiazyne nitrogen with thiol followed by a nucleophilic attack of thiolate anion on the methyl group.
- Yoshimura, Toshiaki,Tsukurimichi, Eiichi,Sugiyama, Yasuhisa,Kita, Hiroshi,Shimasaki, Choichiro,Hasegawa, Kiyoshi
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p. 3176 - 3178
(2007/10/02)
-
- Kinetic Study on the Alkaline Hydrolysis of S,S-Diaryl-N-halosulfilimines
-
Kinetics for the alkaline hydrolysis of S,S-diaryl-N-bromosulfilimines were carried out in aqueous methanol.The observed pseudo-first-order rate constants were found to give a linear correlation with the concentration of sodium hydroxide, k=k1+k2.The first-order rate constants k1 showed a large negative Hammett ρ value (-2.43) for the substituent effect on the phenyl group, nearly zero activation entropy (-0.9+/-13.1 JK-1mol-1) and a relatively large m value (0.638) against the solvent ionizing power Y value suggesting that the reaction process fork1 close to SN1.The salt effect, the deuterium solvent isotope effect and the steric effect are also in accord with the SN1 mechanism.On the other hand, the second order rate constants k2 revealed a small Hammett ρ value, a negative activation entropy (-44.0+/-4.0 JK-1mol-1), a small m value (0.153) and a steric deceleration by ortho substituents showing that the reaction for k2 is SN2-like.The salt effect and the solvent isotope effect are also compatible with the SN2-like mechanism.Meanwhile, the k1 for S,S-diphenyl-N-halosulfilimines remarkably increased in the order of N-iodo N-bromo N-chloro.This reactivity might be due to the lone pair-lone pair repulsion at the reactant state.From these observations, the alkaline hydrolysis of S,S-diaryl-N-halosulfilimines was confirmed to proceed via concurrent two mechanisms, the SN1-like mechanism involving nitridosulfonium cation as an intermediate and the SN2'-like mechanism with the transition state in which the N-X bond cleavage is more progressed than the S-O bond formation with nucleophiles (-OH, -OMe).
- Yoshimura, Toshiaki,Tsukurimichi, Eiichi,Kita, Hiroshi,Fujii, Hiroshi,Shimasaki, Choichiro
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p. 1764 - 1769
(2007/10/02)
-
- Formation of S,S-diphenyl-S-methoxythiazyne Ph2S(OMe)(≡N) in the alkaline hydrolysis of S,S-diphenyl-N-halosulfilimines
-
The structure of a compound formed during the alkaline hydrolysis of S,S-diphenyl-N-halosulfilimines to the corresponding sulfoximine in methanol was assigned to PhS(OMe) (≡N) Ph, S,S-diphenyl-S-methoxythiazyne, on the basis of spectroscopic analyses and chemical reactions.
- Yoshimura,Tsukurimichi,Kita,Fujii,Shimasaki
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p. 6339 - 6340
(2007/10/02)
-
- NUCLEOPHILIC SUBSTITUTION AT TRICOORDINATE SULFUR. HYDROLYSIS OF N-DIARYLSULFONIODIMETHYLSULFOXIMINIUM SALT IN BASIC AQUEOUS ACETONITRILE
-
N-Diarylsulfoniodimethylsulfoximinium salts (Ar2S+-NS(O)Me2X-), prepared by treating diaryl sulfides with N-halodimethylsulfoximinies, were found to be hydrolyzed readily under alkaline conditions to form the corresponding diaryl sulfoxides and dimethylsulfoximine quantitatively.The reaction was found to proceed with inversion of configuration.The kinetic study of the reaction in aqueous acetonitrile was carried out and the reaction was found to follow the second-order rate equation, namely, first-order each in the sulfoniosulfoximinium salt and the base, respectively.Activation parameters, determined for the reaction with N-diphenylsulfoniodimethylsulfoximinium perchlorate were found to be ΔH = 12.2 Kcal*mol-1, ΔS = -17.0 eu.The rate constants of the hydrolyses for the ring-substituted derivatives gave a good correlation with the Hammett's ? constants and gave a ρ value of 3.08.This large ρ value suggests that the reaction involves the formation of the sulfurane intermediate at the rate-determining step of the reaction.
- Kikuchi, Katsuaki,Furukawa, Naomichi,Oae, Shigeru
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p. 291 - 300
(2007/10/02)
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- REACTION OF N-HALOSULFOXIMINES WITH DISULFIDES
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The reaction of S,S-diphenyl-N-chloro-(1), S,S-diphenyl-N-bromo-(2), and S-methyl-S-phenyl-N-chlorosulfoximine (5) with disulfides in refluxing carbon tetrachloride was found to afford the corresponding sulfoxides.In the presence of pyridine, 1 and 2 reacted with disulfides at room temperature to give the corresponding bis-diphenylsulfoximinyl alkyl or aryl sulfonium halides arising from the reaction of the intermediary N-sulfenylated sulfoximine and the starting N-halosulfoximine.
- Akasaka, T.,Furukawa, N.,Oae, S.
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p. 277 - 284
(2007/10/02)
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- CONVENIENT PREPARATION AND SPECTROSCOPIC STUDIES OF SULFOXIMINES AND SULFONEDIIMINES: N-CHLOROSULFILIMINE AS KEY INTERMEDIATE
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N-Unsubstituted sulfilimines, when reacted with sodium hypochlorite in an aqueous alkaline methanol solution or with Chloramine-T in dry acetonitrile in the presence of excess sodium salt of tosylamide were converted to the corresponding N-unsubstituted s
- Furukawa, Naomichi,Akutagawa, Kunihiko,Oae, Shigeru
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- THERMOLYSES AND REACTIONS WITH NUCLEOPHILES OF N-SULFUR-GROUP-SUBSTITUTED SULFOXIMINES
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Thermolyses and reactions with nucleophiles of S,S-diphenylsulfoximines (1) bearing the following N-sulfur-substituents, i.e., N-p-tolylthio-(b), N-p-tolylsulfinyl-(c), N-(N'-p-tolylsulfonyl-p-toluenesulfinimidoyl)-(d), N-(S',S'-diphenylsulfonio)-(e), N-p-tolylsulfonyl-(f), and N-(N'-p-tolylsulfonyl-p-toluenesulfonimidoyl)-(g), have been examined.The former three sulfoximines (1b-d) are thermally unstable and readily decompose to form diphenyl sulfoxide and diphenyl sulfide by the initial cleavage of the S-N linkage in the original sulfoximines.The latter three sulfoximines (1e-g) fairly stable thermally. 1b-d were found to react with several nucleophiles to afford the corresponding sulfenylated, sulfinylated or sulfinimidoylated products together with N-unsubstituted sulfoximine(1a). 1e was found to react with potassium hydroxide/methanol or chloramine-T/N,N-dimethylformamide to afford diphenyl sulfoxide or S,S-diphenyl-(N-p-tolylsulphonyl)sulfilimine along with 1a in good yields.The latter two sulfoximines (1f,g) were found to be inert in the treatment with a few nucleophiles.S,S-Diphenyl-(N-p-tolylthio)-(1b), -(N-p-tolylsulfinyl)-(1c), -(N-p-toluenesulfinimidoyl)-(1d), and -N-(diphenylsulfonio)-(1e) sulfoximines are all new to sulfoximine chemistry and their chemical behavior and reactivity have not been explored.As a preliminary step, thermal decompositions and reactions of these sulfoximines with several nucleophiles have been examined.
- Oae, Shigeru,Akutagawa, Kunihiko,Furukawa, Naomichi
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p. 223 - 234
(2007/10/02)
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- Oxidation of S,S-Diaryl-N-(p-tolylsulfonyl)sulfilimines and N-Unsubstituted S,S-Diaryl-sulfilimines with Potassium Hyperoxide Anion Radical (O2-.) in the Presence of 1-Bromopropane, Benzoyl Chloride, p-Tolylsulfonyl Chloride, Carbon Tetrachloride, Chloroform, or Dichloromethane in
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The reaction of S,S-diaryl-N-(p-tolylsulfonyl)sulfilimines and N-unsubstituted diaryl-sulfilimines with hydroperoxide anion radical (O2-.) in the presence of 18-crown-6 as a catalyst together with 1-bromopropane/benzene, benzoyl chloride/benzene, p-tolylsulfonyl chloride/benzene, carbon tetrachloride, chloroform, or dichloromethane, gave the corresponding sulfoximines, through nucleophilic oxidation with an intermadiary dioxy species formed upon treatment of organic halides with potassium hyperoxide (KO2).
- Akutagawa, Kunihiko,Furukawa, Naomichi,Oae, Shigeru
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p. 1104 - 1107
(2007/10/02)
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- A FACILE CONVERSION OF SULFOXIMINES AND SULFONEDIIMINES TO SULFOXIDES AND SULFILIMINES WITH TERT-BUTYL NITRITE
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N-Unsubstituted sulfoximines and N-mono-tosylsulfonediimines were found to react readily with tert-butyl nitrite to give the corresponding sulfoxides and N-tosylsulfilimines in high yields with no racemization.
- Akutagawa, Kunihiko,Furukawa, Naomichi,Oae, Shigeru
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p. 369 - 374
(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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- Homolytic Reaction of N-Halogenosulphoximides with Olefins and Toluene
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Homolytic addition reaction of N-halogenosulphoximides, i.e. diphenyl-N-chlorosulphoximide (1), diphenyl-N-bromosulphoximide (2), and methylphenyl-N-chlorosulphoximide (3), to olefins such as t-butylethylene and cyclohexene under both u.v. irradiation and thermolysis in the presence of a radical initiator was found to afford the corresponding N-alkylated sulphoximides, which are presumed to be formed via the initial addition of the sulphoximidoyl radical.Meanwhile, homolytic bromination of toluene with N-bromosulphoximide (2) proceeded readily by u.v. irradiation, or by thermal reaction in the presence of a radical initiator, to afford benzyl bromide.However, chlorination of toluene was sluggish with N-chlorosulphoximides (1) and (3). α-Bromination was interpreted in terms of a chain process involving bromine molecules like the 'Goldfinger mechanism', but not via that involving the sulphoximidoyl radical.
- Akasaka, Takeshi,Furukawa, Naomichi,Oae, Shigeru
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p. 1257 - 1261
(2007/10/02)
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