- Metal-free C-Se cross-coupling enabled by photoinduced inter-molecular charge transfer
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Metal-free C-Se cross-couplingsviathe formation of electron-donor-acceptor (EDA) complexes have been developed. The visible-light induced reactions can be applied for the synthesis of a series of unsymmetrical diaryl selenides employing aryl bromides, aryl iodides as well as aryl chlorides under mild reaction conditions. The scale-up was readily achieved. UV-Vis spectroscopy measurements provide insight into the reaction mechanism.
- Rueping, Magnus,Yue, Huifeng,Zhu, Chen,Zhumagazy, Serik
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supporting information
p. 96 - 99
(2021/12/29)
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- Syntheses, characterization, and single crystal X-ray analysis of 2-pyridyl aryl selenium (IV) bromides and chlorides
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In the present work, a variety of symmetrical and unsymmetrical 2-pyridyl aryl selenium (IV) chlorides or bromides were prepared by the dropwise addition of a dilute solution of bromine or sulfuryl chloride to the corresponding 2-pyridyl aryl selenide in dried organic solvent with continuous stirring at 0 °C. Removal of the solvent under reduced pressure resulted in the synthesis of, 2-pyridyl aryl selenium (IV) bromides or chlorides, respectively, in quantitative yields. The titled dihalides prepared were characterized by elemental analysis, spectroscopic studies, and single crystal X-ray analysis. Single crystal X-ray analysis revealed that the 2-pyridyl aryl selenium (IV) bromides/chlorides have a distorted trigonal bipyramidal structure. The pyridyl and phenyl rings along with a lone pair of electrons on selenium are at equatorial positions whereas chloride/bromide atoms at axial positions of the distorted trigonal bipyramidal structure.
- Gujral, Gurjeet,Bhasin, Aman K. K.,Bhasin,Gulati, Shivani
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- Dimsyl Anion Enables Visible-Light-Promoted Charge Transfer in Cross-Coupling Reactions of Aryl Halides
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A methodology is reported for visible-light-promoted synthesis of unsymmetrical chalcogenides enabled by dimsyl anion in the absence of transition-metals or photoredox catalysts. The cross-coupling reaction between aryl halides and diaryl dichalcogenides proceeds with electron-rich, electron-poor, and heteroaromatic moieties. Mechanistic investigations using UV-Vis spectroscopy, time-dependent density functional theory (TD-DFT) calculations, and control reactions suggest that dimsyl anion forms an electron-donor-acceptor (EDA) complex capable of absorbing blue light, leading to a charge transfer responsible for generation of aryl radicals from aryl halides. This previously unreported mechanistic pathway may be applied to other light-induced transformations performed in DMSO in the presence of bases and aryl halides.
- Pan, Lei,Cooke, Maria Victoria,Spencer, Amara,Laulhé, Sébastien
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supporting information
p. 420 - 425
(2021/11/01)
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- Synthesis of 2-Organylchalcogenopheno[2,3-b]pyridines from Elemental Chalcogen and NaBH4/PEG-400 as a Reducing System: Antioxidant and Antinociceptive Properties
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An alternative method to prepare 2-organylchalcogenopheno[2,3-b]pyridines was developed by the insertion of chalcogen species (selenium, sulfur or tellurium), generated in situ, into 2-chloro-3-(organylethynyl)pyridines by using the NaBH4/PEG-4
- Peglow, Thiago J.,Bartz, Ricardo H.,Martins, Carolina C.,Belladona, Andrei L.,Luchese, Cristiane,Wilhelm, Ethel A.,Schumacher, Ricardo F.,Perin, Gelson
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supporting information
p. 1741 - 1751
(2020/08/19)
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- Efficient heterogeneous copper-catalysed C–Se coupling of aryl iodides with symmetrical diselenides towards unsymmetrical monoselenides
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A highly efficient heterogeneous copper(I)-catalysed C–Se coupling of aryl iodides with diaryl diselenides was achieved in dimethylformamide at 110 °C under neutral conditions by using a 10 mol% of bipyridine-functionalised MCM-41-supported copper(I) complex [bpy-MCM-41-CuI] as the catalyst and magnesium as the reductive reagent, yielding a variety of unsymmetrical diaryl selenides in good to excellent yields. This heterogeneous copper catalyst can be easily recovered by a simple filtration of the reaction solution and recycled at least seven times without significant loss of activity.
- Zhao, Ruonan,Yan, Chenyu,Jiang, Yuanyuan,Cai, Mingzhong
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p. 584 - 588
(2018/11/27)
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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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- Glycerol/hypophosphorous acid: An efficient system solvent-reducing agent for the synthesis of 2-organylselanyl pyridines
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We describe herein an efficient and simple method to synthesize 2-organylselanyl pyridines by reactions of 2-chloropyridines with organylselenols, generated in situ by reaction of diorganyl diselenides, using glycerol as solvent and hypophosphorous acid (
- Thurow, Samuel,Webber, Rodrigo,Perin, Gelson,Lenard?o, Eder J.,Alves, Diego
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supporting information
p. 3215 - 3218
(2013/06/27)
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- An efficient copper(I) iodide catalyzed synthesis of diaryl selenides through Cse bond formation using solvent acetonitrile as ligand
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A wide range of diaryl selenides can be synthesized through CSe bond formation using readily available copper(I) iodide as catalyst under mild reaction conditions (82C) from aryl iodides and diphenyl diselenide. In this coupling reaction, solvent acetonitrile acts as ligand for copper(I) iodide and no external ligand is required. Less reactive aryl bromides also provide the di-aryl selenides in good isolated yields. Georg Thieme Verlag Stuttgart ? New York.
- Dandapat, Arpan,Korupalli, Chiranjeevi,Prasad,Singh, Rahul,Sekar, Govindasamy
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experimental part
p. 2297 - 2302
(2011/09/16)
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- CuS/Fe: A novel and highly efficient catalyst system for coupling reaction of aryl halides with diaryl diselenides
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The CuS catalyzed coupling reactions of aryl halides and diaryl diselenides were accelerated by the addition of Fe powder in only 3-12 h with good to excellent yields. SEM-EDX indicated that the in situ iron oxides as support against catalyst agglomeration accelerated the reaction. This catalyst system was also demonstrated recyclable without significant loss of catalytic activity.
- Li, Yaming,Wang, Huifeng,Li, Xiaoying,Chen, Tao,Zhao, Defeng
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supporting information; experimental part
p. 8583 - 8586
(2010/11/17)
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- Synthesis of unsymmetrical pyridyl aryl selenides by the reductive cleavage of SeSe bond
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An efficient protocol for the synthesis of novel hitherto unknown substituted and unsubstituted phenyl pyridyl selenides from dipyridyl/diphenyl diselenides and phenyl/pyridyl halides in the presence of copper catalysed system, Cu2O/Mg/bpy is being presen
- Bhasin,Doomra, Shivani,Kaur, Gurjeet,Arora, Ekta,Singh, Neelam,Nagpal, Yogesh,Kumar, Rajeev,Rishu,Klapoetke,Mehta
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experimental part
p. 992 - 997
(2009/04/07)
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- CsOH·H2O promoted areneselenenylation of aryl bromides and iodides
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We report a transition metal-free synthetic protocol for the cross-coupling reaction of aryl bromides and aryl iodides and diphenyl diselenide (Ph 2Se2) using CsOH·H2O as a base in DMSO at 110°C. Using this protocol, we show that a variety of diaryl selenides can be synthesized in moderate to good yields.
- Varala, Ravi,Ramu, Enugala,Adapa, Srinivas R.
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p. 140 - 141
(2007/10/03)
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- Magnesium-Induced Copper-Catalyzed Synthesis of Unsymmetrical Diaryl Chalcogenide Compounds from Aryl Iodide via Cleavage of the Se-Se or S-S Bond
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The methodology for a copper-catalyzed preparation of diaryl chalcogenide compounds from aryl iodides and diphenyl dichalcogenide molecules is reported. Unsymmetrical diaryl sulfide or diaryl selenide can be synthesized from aryl iodide and PhYYPh (Y = S, Se) with a copper catalyst (CuI or Cu2O) and magnesium metal in one pot. This reaction can be carried out under neutral conditions according to an addition of magnesium metal as the reductive reagent. Furthermore, it is efficiently available for two monophenylchalcogenide groups generated from diphenyl dichalcogenide.
- Taniguchi, Nobukazu,Onami, Tetsuo
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p. 915 - 920
(2007/10/03)
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- Copper-catalyzed synthesis of diaryl selenide from aryl iodide and diphenyl diselenide using magnesium metal
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Various unsymmetrical diaryl selenides can be synthesized from aryl iodides and diphenyl diselenide by an addition of magnesium metal in the presence of a copper catalyst. This method can exploit efficiently two phenylselenide-molecules generated from diphenyl diselenide under neutral conditions.
- Taniguchi, Nobukazu,Onami, Tetsuo
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p. 829 - 832
(2007/10/03)
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- A new and convenient route to 2,2′-dipyridyl diselenide/ditelluride and some of their alkyl/aryl derivatives through BF3-complexed pyridyl carbanion
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Synthesis of 2,2′-dipyridyl diselenide/ditelluride and some alkyl/aryl pyridyl selenide/telluride is reported.
- Bhasin,Bhandal,Singh,Singh,Singh,Singh
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p. 1319 - 1325
(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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- The selective functionalization of saturated hydrocarbons. Part 33. Further reactions which take place in the Fe(II)-Fe(IV) manifold
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Utilization of the Fe(II)-H2O2 system in the presence of diphenyl diselenide, phenylselenol, diphenyl disulfide and thiophenol converts saturated hydrocarbons into the corresponding alkyl phenyl selenide or alkyl phenyl sulfide. Star
- Barton, Derek H. R.,Chabot, Beatrice M.
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p. 10287 - 10300
(2007/10/03)
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- THE SYNTHESIS OF BIS(PHENYLSELENENYL), BIS(ALKYELSELENENYL)PYRIDINES AND OF PYRIDYLSELENOLATE ANIONS
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The reactions of several dihalogenopyridines with PhSeNa or MeSeLi in DMF afforded the monosubstitution products in good yields.With excess PhSeNa the bis(phenylselenenyl)pyridines were easily obtained, Whereas with excess MeSeLi the initially formed halo
- Tiecco, Marcello,Testaferri, Lorenzo,Tingoli, Marco,Chianelli, Donatella,Bartoli, Donatelle,Balducci, Roberta
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p. 4883 - 4894
(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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