- A Mild Heteroatom (O -, N -, and S -) Methylation Protocol Using Trimethyl Phosphate (TMP)-Ca(OH) 2Combination
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A mild heteroatom methylation protocol using trimethyl phosphate (TMP)-Ca(OH)2combination has been developed, which proceeds in DMF, or water, or under neat conditions, at 80 °C or at room temperature. A series of O-, N-, and S-nucleophiles, including phenols, sulfonamides, N-heterocycles, such as 9H-carbazole, indole derivatives, and 1,8-naphthalimide, and aryl/alkyl thiols, are suitable substrates for this protocol. The high efficiency, operational simplicity, scalability, cost-efficiency, and environmentally friendly nature of this protocol make it an attractive alternative to the conventional base-promoted heteroatom methylation procedures.
- Tang, Yu,Yu, Biao
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- INDOLE DERIVATIVE USED AS CRTH2 INHIBITOR
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The present application discloses an indole as represented by formula (I) used as a CRTH2 inhibitor, and a pharmaceutically acceptable salt or tautomer of the indole, and an application of same in treating a disease related to a CRTH2 receptor.
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- Visible light-promoted formation of C-B and C-S bonds under metal- A nd photocatalyst-free conditions
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A green, efficient, photoinduced synthesis of arylboronic esters and aryl sulfides has been developed. Bench stable arylazo sulfones were used as radical precursors for a photocatalyst- A nd additive-free carbon-heteroatom bond formation under visible light. The protocols are applicable to a wide range of substrates, providing products in good yields.
- Blank, Lena,Fagnoni, Maurizio,Protti, Stefano,Rueping, Magnus
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p. 1243 - 1252
(2019/02/26)
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- Indole derivative serving as CRTH2 inhibitor
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The invention discloses an indole derivative serving as a CRTH2 inhibitor shown as a formula (I) as shown in the specification or pharmaceutically acceptable salts, as well as application of the indole derivative in treatment of diseases related to the CR
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- Copper-catalyzed decarboxylative methylthiolation of aromatic carboxylate salts with DMSO
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A novel copper-catalyzed decarboxylative methylthiolation of arenecarboxylate salts has been realized using DMSO as the methylthiolation source. Various potassium aryl carboxylates underwent decarboxylative methylthiolation under air to furnish the corresponding aryl methyl thioethers in moderate to excellent yields. The reaction tolerated a wide variety of functional groups. Notably, the synthesis of ethylthioethers was also successfully achieved directly from diethyl sulfoxide under similar reaction conditions.
- Hu, Liang,Wang, Dadian,Chen, Xiang,Yu, Lin,Yu, Yongqi,Tan, Ze,Zhu, Gangguo
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supporting information
p. 5674 - 5679
(2017/07/22)
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- A practical and chemoselective Mo-catalysed sulfoxide reduction protocol using a 3-mercaptopropyl-functionalized silica gel (MPS)
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A convenient sulfoxide deoxygenation procedure using a mercaptopropyl-functionalized silica gel as the reducing agent is described. This new protocol based on a heterogeneous reagent displays broad scope and tolerance to reducible functional groups and, from an experimental point of view, enhances previous methods by simplifying the isolation of the sulfide to a simple filtration.
- García, Nuria,Fernández-Rodríguez, Manuel A.,García-García, Patricia,Pedrosa, María R.,Arnáiz, Francisco J.,Sanz, Roberto
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p. 27083 - 27086
(2016/03/25)
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- Metal-free radical thiolations mediated by very weak bases
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Aromatic thioethers and analogous heavier chalcogenides were prepared by reaction of arene-diazonium salts with disulfides in the presence of the cheap and weak base NaOAc. The mild and practical reaction conditions (equimolar reagents, DMSO, r.t., 8 h) tolerate various functional groups (e.g. Br, Cl, NO2, CO2R, OH, SCF3, furans). Mechanistic studies indicate the operation of a radical aromatic substitution mechanism via aryl, acetyloxyl, thiyl, and dimsyl radicals.
- Koziakov, Denis,Majek, Michal,Jacobi Von Wangelin, Axel
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supporting information
p. 11347 - 11352
(2016/12/16)
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- Synthesis and characterization of ortho-thio-functionalized triarylmethyl palladium complexes
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A series of triarylmethyl palladium complexes with ortho coordination sites were synthesized. Thereby, the palladium atom exhibits various inter- and intramolecular binding modes towards the organic ligand. Further, the first crystallographically proven, exclusively σ-coordinated triarylmethyl palladium complexes, stabilized by ortho-thio-substituents, were discovered. The NMR spectra of the palladium complexes indicate temperature-dependent dynamic behavior.
- Sch?ler, Stephan,Merz, Klaus,Puls, Arik,Winter, Manuela,Dyker, Gerald
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- A diphenyl ether derived bidentate secondary phosphine oxide as a preligand for nickel-catalyzed C-S cross-coupling reactions
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A new bidentate secondary phosphine oxide (SPO) was synthesized from diphenyl ether via ortho-lithiation, phosphorylation with PhP(Cl)NEt2, and hydrolysis in an acidic medium. Nickel(0) species ligated with this new SPO was established as a mor
- Wellala, Nadeesha P. N.,Guan, Hairong
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p. 10802 - 10807
(2015/11/17)
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- An unprecedented use for glycerol: Chemoselective reducing agent for sulfoxides
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A new application for glycerol that expands its possibilities beyond a green solvent and a precursor of value-added products has been demonstrated. Simple, easily available, and environmentally friendly dioxomolybdenum(vi) complexes are highly efficient catalysts for the chemoselective sulfoxide deoxygenation with this biomass-derived chemical feedstock. Both refined glycerol and crude glycerin can be used, thus expanding the potential application of this reaction. Subsequent transformation of glycerol during this reductive process has also been investigated.
- Garcia, Nuria,Garcia-Garcia, Patricia,Fernandez-Rodriguez, Manuel A.,Garcia, Daniel,Pedrosa, Maria R.,Arnaiz, Francisco J.,Sanz, Roberto
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supporting information
p. 999 - 1005
(2013/07/25)
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- Organocatalytic visible light mediated synthesis of aryl sulfides
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Photo-sensitized synthesis of arylsulfides from arenediazonium salts in the presence of eosin Y has been developed. This protocol exhibits high functional group tolerance and a wide substrate scope and is an attractive alternative to the thermal reaction that involves explosive intermediates.
- Majek, Michal,Von Wangelin, Axel Jacobi
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supporting information
p. 5507 - 5509
(2013/06/27)
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- Copper-mediated methylthiolation of aryl halides with DMSO
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A copper-mediated methylthiolation of aryl halides with the widely available DMSO is described. The procedure tolerates a series of functional groups such as methoxy, nitro, chloro, fluoro, trifluoromethyl, formyl and methoxycarbonyl groups. Thus, it represents a simple and facile methylthiolation procedure.
- Luo, Fang,Pan, Changduo,Li, Liping,Chen, Fan,Cheng, Jiang
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supporting information; experimental part
p. 5304 - 5306
(2011/06/21)
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- Syntheses, structures, and catalytic activities of hemilabile thioether-functionalized NHC complexes
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Four imidazolium (5a/b) and benzimidazolium (6a/b) salts with hemilabile alkyl-aryl thioether functions have been prepared via a straightforward and modular pathway in order to compare their reactivities toward palladation. Reaction of 5a/b with Pd(OAc)s
- Huynh, Han Vinh,Yeo, Chun Hui,Chew, Ying Xia
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experimental part
p. 1479 - 1486
(2010/05/15)
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- N-(2-Alkoxycarbonylbenzenesulfeny)benzimidazoles as nitrogen-, sulfur-, and carbon-sulfenylation reagents
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N-(2-Alkoxycarbonylbenzenesulfenyl)benzimidazoles reacted with nucleophiles such as amides, imidates, thiols, Grignard reagents, and active methylene compounds to yield the corresponding sulfenylated products: N-acylsulfenamides, N-sulfenylimidates, disulfides, sulfides, and sulfenylated active methylene compounds, respectively.
- Shimizu, Masao,Fukazawa, Hidenori,Inoue, Jun'ichi,Abe, Yoshimoto,Konakahara, Takeo
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- Hemilabile behavior of a thioether-functionalized N-heterocyclic carbene ligand
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The truely hemilabile nature of a novel thioether-functionalized N-heterocyclic carbene ligand is demonstrated in a range of Pd(ii) complexes. The Royal Society of Chemistry 2006.
- Huynh, Han Vinh,Yeo, Chun Hui,Tan, Geok Kheng
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p. 3833 - 3835
(2007/10/03)
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- Highly chemoselective methylation and esterification reactions with dimethyl carbonate in the presence of NaY faujasite. The case of mercaptophenols, mercaptobenzoic acids, and carboxylic acids bearing OH substituents
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In the presence of NaY faujasite, the reactions of dimethyl carbonate (DMC) with several ambident nucleophiles such as o- and p-mercaptophenols (1a,b), o- and p-mercaptobenzoic acids (2a,b), o- and p-hydroxybenzoic acids (3a,b), mandelic and phenyllactic acids (4, 5), have been explored under batch conditions. Highly chemoselective reactions can be performed: at 150 °C, compounds 1 and 2 undergo only a S-methylation reaction, without affecting OH and CO2H groups; at 165 °C, acids 3-5 form the corresponding methyl esters, while both their aromatic and aliphatic OH substituents are fully preserved from methylation and/or transesterification processes. Typical selectivities are of 90-98% and isolated yields of products (S-methyl derivatives and methyl esters, respectively) are in the range of 85-96%. A comparative study with K2CO3 as a catalyst is also reported. Although the base (K2CO3) turns out to be more active than the zeolite, the chemoselectivity is elusive: compounds 2a,b undergo simultaneous S-methylation and esterification reactions, and acids 3-5 yield complex mixtures of products of O-methylation, O-methoxycarbonylation, and esterification of their OH and CO2H groups, respectively. Overall, the combined use of a nontoxic reagent/solvent (DMC) and a safe promoter (NaY) imparts a genuine ecofriendly nature to the investigated synthesis.
- Selva, Maurizio,Tundo, Pietro
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p. 1464 - 1470
(2007/10/03)
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- Behavioral approach to nondyskinetic dopamine antagonists: Identification of Seroquel
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A great need exists for antipsychotic drugs which will not induce extrapyramidal symptoms (EPS) and tardive dyskinesias (TDs). These side effects are deemed to be a consequence of nonselective blockade of nigrostriatal and mesolimbic dopamine D2 receptors. Nondyskinetic clozapine (1) is a low-Potency D2 dopamine receptor antagonist which appears to act selectively in the mesolimbic area. In this work dopamine antagonism was assessed in two mouse behavioral assays: antagonism of apomorphine-Induced climbing and antagonism of apomorphine-Induced disruption of swimming. The potential for the liability of dyskinesias was determined in haloperidol-Sensitized Cebus monkeys. Initial examination of a few close cogeners of I enhanced confidence in the Cebus model as a predictor of dyskinetic potential. Considering dibenzazepines, 2 was not dyskinetic whereas 2a was dyskinetic. Among dibenzodiazepines, 1 did not induce dyskinesias whereas its N-2-(2-Hydroxyethoxy)ethyl analogue 3 was dyskinetic. The emergence of such distinctions presented an opportunity. Thus, aromatic and N-Substituted analogues of 6-(piperazin-1-yl)-11H-Dibenz[b,e]azepines and 11-(piperazin-1-yl)dibenzo[b,f][1,4]-thiazepines and -Oxazepines were prepared and evaluated. 11-(4-[2-(2-Hydroxyethoxy)ethyl]-piperazin-1-yl)dibenzo[b,f][1,4]thiazepine (23) was found to be an apomorphine antagonist comparable to clozapine. It was essentially nondyskinetic in the Cebus model. With 23 as a platform, a number of N-Substituted analogues were found to be good apomorphine antagonists but all were dyskinetic.
- Warawa,Migler,Ohnmacht,Needles,Gatos,McLaren,Nelson,Kirkland
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p. 372 - 389
(2007/10/03)
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- Thiol-dependent DNA cleavage by 3H-1,2-benzodithiol-3-one 1,1-dioxide
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Hydrodisulfides (RSSH) have previously been implicated as key intermediates in thiol-triggered oxidative DNA damage by the antitumor agent leinamycin. In an effort to better understand DNA damage by RSSH and to expand on the number and type of chemical systems that produce this reactive intermediate, the ability of 3H-1,2-benzodithiol-3-one 1,1-dioxide (11) to serve as a thio-dependent DNA cleaving agent has been investigated. The findings reported here indicate that reaction of 11 with thiols results in release of RSSH and subsequent oxidative DNA strand cleavage. (C) 2000 Elsevier Science Ltd. All rights reserved.
- Breydo, Leonid,Gates, Kent S.
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p. 885 - 889
(2007/10/03)
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- Asymmetric oxidation catalyzed by myoglobin mutants
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The sperm whale myoglobin active site mutants (L29H/H64L and F43H/H64L Mb) have been shown to catalyze the asymmetric oxidation of sulfides and olefins. Thioanisole, ethyl phenyl sulfide, and cis-β-methylstyrene are oxidized by L29H/H64L Mb with more than
- Ozaki, Shin-Ichi,Yang, Hui-Jun,Matsui, Toshitaka,Goto, Yoshio,Watanabe, Yoshihito
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p. 183 - 192
(2007/10/03)
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- Flash vacuum pyrolysis of stabilised phosphorus ylides. Part 12. Extrusion of Ph3P from sulfonyl ylides and reactivity of the resulting sulfonyl carbenes
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Twelve sulfonyl stabilised phosphorus ylides have been prepared and their behaviour upon flash vacuum pyrolysis at 600°C has been examined. Examples with an arylsulfonyl substituent undergo loss of Ph3PO to give intractable products but those with an arylmethylsulfonyl substituent separately lose Ph3P and SO2 to give products consistent with the intermediacy of sulfonyl carbenes. X-Ray structure determinations of one ylide from each series show a more significant P-O non-bonding interaction in the first case, providing some explanation for the different thermal reactivity.
- Aitken, R. Alan,Drysdale, Martin J.,Ferguson, George,Lough, Alan J.
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p. 875 - 880
(2007/10/03)
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- Asymmetric sulfoxidation catalyzed by a vanadium bromoperoxidase: Substrate requirements of the catalyst
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An investigation of the catalytic effect of vanadium bromoperoxidase (VBrPO, from Corallina officinalis) on the oxidation of a series of prochiral sulfides by hydrogen peroxide, revealed that substrates having a cis- positioned carboxyl group are oxidized
- Andersson, Malin A.,Allenmark, Stig G.
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p. 15293 - 15304
(2007/10/03)
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- Alkylation Reactions by Means of Alkanols and Carbon Monoxide: An Efficient Synthesis of Thioethers and of Caffeine from Theophylline
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The reaction of sodium or potassium thiolates with alkanols and carbon monoxide provides a versatile route to produce thioethers in excellent yields.By analogy, the potassium salt of theophylline suffers a nearly quantitative conversion to caffeine when heated with methanol under CO pressure.The mechanism of these alkylation reactions is discussed. - Key Words: Nucleophilic alkylation / Thioethers / Caffeine / Carbon monoxide / Alkanols
- Bott, Kaspar
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p. 1955 - 1956
(2007/10/02)
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- Sulfonamides and uses
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Sulfonamides of formula I, in which the symbols R1 -R6, X, Y and n have the significance given in the description and which are in part novel compounds, and salts thereof, which can be used as active ingredients for the manufacture of medicaments for the treatment of circulatory disorders, especially hypertension, ischemia, vasospasms and angina pectoris, are described.
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- Electroreduction of Organic Compounds, 13. - Coelectroreduction of Methyl Dithiocarboxylates with Halogenoarenes
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Coelectroreduction of methyl dithiopivalate (1) or dithiobenzoate (11) with a monohalogenobenzene does not result in any characteristic products.However, the aryl methyl dithioacetals 7 and 8 are formed on cathodic reduction of 1 in the presence of the o-dihalogenobenzenes 4 and 5, respectively. - An SNAr mechanism is proposed, which is also in accordance with the formation of 2-bromobenzenethiolate (9) from 1 and 4 or 5.
- Streek, Michael,Voss, Juergen
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p. 2251 - 2254
(2007/10/02)
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- Syntheses of Mercaptobenzoic Acids and Mercaptopyridines Using Elemental Sulfur in the Presence of NaOH-KOH
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Mercaptobenzoic acids and mercaptopyridines were synthesized by using mercaptylation of halogeno compounds with elemental sulfur in the presence of molten salts (NaOH-KOH).This procedure was also applied to the preparation of selenoaryl compounds by using elemental selenium.Based on the behavior of the molten salts and sulfur, Na2S and K2S were considered to be the active species for the mercaptylation.KEYWORDS-mercaptylation; molten salt; o-mercaptobenzoic acid; o-selenobenzoic acid; 2-mercaptopyridine
- Kamiyama, Tsutomu,Enomoto, Saburo,Inoue, Masami
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p. 5184 - 5189
(2007/10/02)
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