- Nickel Phosphite/Phosphine-Catalyzed C-S Cross-Coupling of Aryl Chlorides and Thiols
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A method for the coupling of aryl chlorides and thiophenols using an air-stable nickel(0) catalyst is described. This thioetherification procedure can be effectively applied to a range of electronically diverse aryl/heteroaryl chlorides without more expensive metal catalysts such as palladium, iridium, or ruthenium. This investigation also illustrates both, a variety of thiol coupling partners and, in certain cases, the use of Cs2CO3.
- Jones, Kieran D.,Power, Dennis J.,Bierer, Donald,Gericke, Kersten M.,Stewart, Scott G.
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supporting information
p. 208 - 211
(2018/01/17)
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- PRODUCTION METHOD FOR BI(HETERO)ARYL(THIO)ETHER COMPOUND
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PROBLEM TO BE SOLVED: To provide a method for synthesizing a bi(hetero)aryl(thio)ether compound at low cost without discharging halogen-derived waste. SOLUTION: The production method includes, for example as shown in the following formula, reacting a (thio)ester compound represented by formula (1) in the presence of a nickel catalyst (or a palladium catalyst) as well as a ligand compound to produce bi(hetero)aryl(thio)ether compound represented by formula (2). [Ar and Ar' are each independently a substituted/unsubstituted aryl group or heteroaryl group; Y is O or S.]. SELECTED DRAWING: None COPYRIGHT: (C)2017,JPOandINPIT
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Paragraph 0111-0114; 0116-0117
(2017/10/31)
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- Efficient synthesis of unsymmetrical heteroaryl thioethers and chalcogenides by alkali hydroxide-mediated SNAr reactions of heteroaryl halides and dichalcogenides
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An efficient alkali hydroxide-mediated SNAr reaction of heteroaryl halides has been developed for the practical synthesis of the useful unsymmetrical heteroaryl thioethers and chalcogenides. The usually odorless, easily available, lowly toxic, and easily stored and handled diorganyl dichalcogenides can be used as safer and convenient chalcogen nucleophile precursors and diverse unsymmetrical heteroaryl chalcogenides can be obtained in good to high yields by the method.
- Ma, Xiantao,Liu, Quan,Jia, Xiaojuan,Su, Chenliang,Xu, Qing
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p. 56930 - 56935
(2016/07/06)
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- Thioetherification of Chloroheteroarenes: A Binuclear Catalyst Promotes Wide Scope and High Functional-Group Tolerance
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A constrained binuclear palladium catalyst system affords selective thioetherification of a wide range of functionalized arenethiols with chloroheteroaromatic partners with the highest turnover numbers (TONs) reported to date and tolerates a large variety of reactive functions. The scope of this system includes the coupling of thiophenols with six- and five-membered 2-chloroheteroarenes (i.e., functionalized pyridine, pyrazine, quinoline, pyrimidine, furane, and thiazole) and 3-bromoheteroarenes (i.e., pyridine and furane). Electron-rich congested thiophenols and fluorinated thiophenols are also suitable partners. The coupling of unprotected amino-2-chloropyridines with thiophenol and the successful employment of synthetically valuable chlorothiophenols are described with the same catalyst system. DFT studies attribute the high performance of this binuclear palladium catalyst to the decreased stability of thiolate-containing resting states. Palladium loading was as low as 0.2 mol %, which is important for industrial application and is a step forward in solving catalyst activation/deactivation problems.
- Platon, Mélanie,Wijaya, Novi,Rampazzi, Vincent,Cui, Luchao,Rousselin, Yoann,Saeys, Mark,Hierso, Jean-Cyrille
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p. 12584 - 12594
(2016/08/25)
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- Sulfur-silicon bond activation catalysed by Cl/Br ions: Waste-free synthesis of unsymmetrical thioethers by replacing fluoride catalysis and fluorinated substrates in SNAr reactions
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In contrast to conventional activation of Nu-SiR3 reagents by F ion attributed to the strong affinity of Si to F, S-Si activation can now be achieved using Cl/Br ions of TBAX as catalysts via formation of weaker X-Si bonds and Me3Si-X. This led to a waste-free synthesis of unsymmetrical thioethers via F-free SNAr reactions of activated (hetero)aryl halides and RS-SiMe3, with recovery of the useful Me3Si-X reagent in high yields. This journal is the Partner Organisations 2014.
- Jia, Xiaojuan,Yu, Lei,Liu, Jianping,Xu, Qing,Sickert, Marcel,Chen, Lianhui,Lautens, Mark
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supporting information
p. 3444 - 3449
(2014/07/08)
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- Microwave-assisted synthesis of quinoline, isoquinoline, quinoxaline and quinazoline derivatives as CB2 receptor agonists
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Quinoline, isoquinoline, quinoxaline, and quinazoline derivatives were synthesized using microwave-assisted synthesis and their CB1/CB2 receptor activities were determined using the [35S]GTPγS binding assay. Most of the prepared quinoline, isoquinoline, and quinoxalinyl phenyl amines showed low-potency partial CB2 receptor agonists activity. The most potent CB2 ligand was the 4-morpholinylmethanone derivative (compound 40e) (-log EC 50 = 7.8; Emax = 75%). The isoquinolin-1-yl(3- trifluoromethyl-phenyl)amine (compound 26c) was a high efficacy CB2 agonist (-log EC50 = 5.8; Emax = 128%). No significant CB1 receptor activation or inactivation was shown in these studies, except 40e, which showed weak CB1 agonist activity (CB1 -log EC50 = 5.0). These ligands serve as novel templates for the development of selective CB2 receptor agonist.
- Saari, Raimo,T?rm?, Jonna-Carita,Nevalainen, Tapio
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experimental part
p. 939 - 950
(2011/03/19)
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- Ring opening of pymisyl-protected aziridines with organocuprates
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The pyrimidine-2-sulfonyl (pymisyl) group is introduced as a new protecting group that can be used to activate aziridines towards ring opening. It is readily introduced and removed under mild conditions. Regioselective ring opening of pymisyl-protected 2-methyl-aziridine with organocuprates gives the corresponding sulfonamides in high yields, and the pymisyl group can subsequently be removed upon treatment with a thiolate. The versatility of this new nitrogen protecting group is illustrated with a new synthesis of Selegiline, a monoamine oxidase-B inhibitor marketed for the treatment of Parkinson's disease. Easy on'easy off: The pymisyl group is introduced as a new protecting group for the activation of aziridines towards ring opening with organocuprates (see scheme). It is readily removed under very mild conditions with thiolates. The versatility of the approach is illustrated in a new synthesis of Selegiline, a drug marketed for the treatment of Parkinson's disease.
- Bornholdt, Jan,Felding, Jakob,Clausen, Rasmus P.,Kristensen, Jesper L.
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supporting information; experimental part
p. 12474 - 12480
(2010/12/25)
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- Catalyst-free and base-free water-promoted SNAr reaction of heteroaryl halides with thiols
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A simple and efficient route for the synthesis of biaryl sulfides have been developed in aqueous medium under base- and catalyst-free conditions. A wide variety of heteroaryl halides and thiols underwent SNAr reaction to provide diaryl sulfides in good to excellent yields. The remarkable key features of the reaction include the use of water as an inexpensive and environmentally benign reaction medium, absence of any additional reagent or catalyst, and easy isolation of the products. Georg Thieme Verlag Stuttgart.
- Sreedhar,Surendra Reddy,Amarnath Reddy
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experimental part
p. 1732 - 1738
(2009/12/26)
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- Green chemical synthesis of 2-benzenesulfonyl-pyridine and related derivatives
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A practical synthesis of 2-benzenesulfonylpyridine, 1, is described which is a key starting material for the manufacture of an investigational new drug candidate at Eli Lilly and Company. An optimized green chemical process was developed which features a novel tandem SNAr/oxidation under mild conditions to produce the target sulfone, 1, in 86% yield and>99% purity. In addition, this novel, environmentally friendly methodology was found to be general for the synthesis of substituted aromatic pyridyl sulfides and sulfones.
- Trankle, William G.,Kopach, Michael E.
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supporting information
p. 913 - 917
(2012/12/30)
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- Tributylmagnesium ate complex-mediated bromine-magnesium exchange of bromoquinolines: A convenient access to functionalized quinolines
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2-, 3- and 4-bromoquinolines were converted to the corresponding lithium tri(quinolyl)magnesates at -10°C by treatment with Bu3MgLi in THF or toluene. The resulting organomagnesium derivatives were quenched by various electrophiles to afford functionalized quinolines.
- Dumouchel, Sylvain,Mongin, Florence,Trécourt, Fran?ois,Quéguiner, Guy
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p. 2033 - 2035
(2007/10/03)
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- Synthesis and reactivity of lithium tri(quinolinyl)magnesates
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2-, 3- and 4-Bromoquinolines were converted to the corresponding lithium tri(quinolinyl)magnesates at -10°C when exposed to Bu3MgLi in THF. The resulting organomagnesium derivatives were quenched with various electrophiles or involved in metal-catalyzed coupling reactions with heteroaryl halides to afford functionalized quinolines.
- Dumouchel, Sylvain,Mongin, Florence,Trécourt, Fran?ois,Quéguiner, Guy
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p. 8629 - 8640
(2007/10/03)
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- Heteroaromatic thioether-organostannane cross-coupling.
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[reaction: see text] Heteroaromatic thioethers and aryl, heteroaryl, and alkenylstannanes participate in a palladium-catalyzed, copper(I)-mediated cross-coupling reaction at 50 degrees C in THF.
- Egi, Masahiro,Liebeskind, Lanny S
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p. 801 - 802
(2007/10/03)
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- Efficient nucleophilic substitution reactions of quinolyl and isoquinolyl halides with nucleophiles under focused microwave irradiation
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Nucleophilic substitution reactions of 2-chloroquinoline, 3-bromoquinoline and 4-bromoisoquinoline with thiolate, alkoxy ions and aniline were completed within several minutes under microwave irradiation. This method gives the desired products with yields up to 99% in a short reaction time, and is superior to the classical heating process.
- Cherng, Yie-Jia
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p. 1125 - 1129
(2007/10/03)
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- SRN1 reaction of haloarenes with benzenethiolate, benzeneselenolate, and benzenetellurolate ions promoted by Sml2
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SRN1 reaction is of haloarenes with benzenethiolate, benzeneselenate, and benzenetellurolate ions can be carried out by use of samarium diiodide (SmI2) as a promoter in DMF-THF to afford the corresponding ArZPh compounds in moderate to good yields.
- Zhang, Yongmin
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p. 539 - 541
(2007/10/03)
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- Nucleophile and Aryl Radical Reactivity in SRN1 Aromatic Nucleophilic Substitution Reactions. Absolute and Relative Electrochemical Determination
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Three electrochemical methods are used to obtain the rate of the Ar.+Nu- reaction.In the direct cyclic voltammetric method, the data are derived from the decrease of the substrate peak current upon addition of the nucleophile while in the relative method they are obtained from the peak heights of the two substitution products observed upon repetitive cycling of the substrate solution in the presence of two nucleophiles.In the redox catalysis method , the reduction of the substrate is catalyzed by an exogeneous reversible couple and the data are derived from the decrease of the catalytic current upon addition of the nucleophile.All three methods were combined to determine the reactivities of a series 26 aryl radical-nucleophile couples.In most cases, the rate constant is close to the diffusion limit.The exceptions concern the 2-quinolyl and 2-pyridyl radicals.The results are discussed in terms of energy difference between the ?* and ?* orbitals in the driving force of the reaction as related to characteristic standard potentials and bond energies.
- Amatore, Christian,Oturan, Mehmet A.,Pinson, Jean,Saveant, Jean-Michel,Thiebault, Andre
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p. 3451 - 3459
(2007/10/02)
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- Relative Reactivities of Nucleophiles Derived from Group 6A toward Aryl Radicals
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Competition experiments have been carried out in liquid ammonia at reflux temperature to determine the relative rate constants for the coupling reactions of nucleophiles derived from group 6A of the periodic table toward aryl radicals.The nucleophiles studied were of type PhZ- (Z=S, Se, Te).It has been proposed that these nucleophiles react under photochemical stimulation with haloaromatic substrates through the SRN1 mechanism of aromatic substitution.The experimental results suggest that the coupling reaction aryl radical-PhZ- anion can be reversible or irreversible depending on the nature of the aryl moiety and the PhZ- nucleophile.Relative rate constants have been determined under conditions of irreversible coupling of the nucleophiles PhZ- (Z=S, Se, Te) with 2-quinolyl radicals.Results here reported indicate an increasing reactivity as we go down the group: PhO- (0.0), PhS- (1.00), PhSe- (5.8), PhTe- (28).The relative rate constant when one of the coupling reactions is reversible supports our mechanistic suggestions.
- Pierini, Adriana B.,Penenory, Alicia B.,Rossi, Roberto A.
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p. 486 - 490
(2007/10/02)
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