- Palladium Complex Immobilized on Magnetic Nanoparticles Modified with 2-Aminopyridine Ligand: A Novel and Efficient Recoverable Nanocatalyst for C–S and C–Se Coupling Reactions
-
A novel, versatile and efficient magnetically recoverable palladium nanocatalyst [Fe3O4@SiO2/2-aminopyridine-Pd(II)] was fabricated via the immobilization of palladium(II) complex on the surface of magnetic nanoparticles modified with 2-aminopyridine ligand. The structure of the as-fabricated Fe3O4@SiO2/2-aminopyridine-Pd(II) nanocomposite was characterized by a series of spectroscopic techniques including FT-IR, SEM, TEM, EDX, TGA, XRD, VSM and ICP-OES techniques. The Fe3O4@SiO2/2-aminopyridine-Pd(II) nanocomposite was utilized under mild and eco-friendly conditions in C–S and C–Se coupling reactions to afford a vast variety of diaryl sulfides and diaryl selenides with good to excellent yields. This heterogeneous palladium catalyst can be magnetically separated and reused for at least 7 consecutive trials without any reduction in activity. Graphical Abstract: [Figure not available: see fulltext.]
- Lu, Lu,Luo, Jia,Wang, Weiqi,Xu, Xiaoqing,Zhang, Jingzheng
-
-
- Photocatalyst-free photoredox synthesis of diaryl selenides by reaction of diselenides with aryldiazo sulfones
-
A photcatalyst-free photoredox synthesis of diaryl selenides has been developed by coupling reaction of diselenides with aryldiazo sulfones. The reaction was accelerated under visible light irradiation without using a photocatalyst or photosensitizer. This approach facilitates the synthesis of diaryl selendes with a wide range of functional group tolerance.
- Jang, Jihoon,Kim, Rabin,Kim, Dae Young
-
supporting information
p. 720 - 726
(2020/11/30)
-
- Trichloroisocyanuric Acid-Promoted Synthesis of Arylselenides and Aryltellurides from Diorganyl Dichalcogenides and Arylboronic Acids at Ambient Temperature
-
A transition-metal-free method for the synthesis of arylselenides and aryltellurides has been established based on the oxidative cross-coupling between diorganyl dichalcogenides and aryl boronic acids. With trichloroisocyanuric acid as an oxidant, the reaction proceeded smoothly to afford the desired products in 45–97% yields at ambient temperature. Three reaction reagents used in this method are stoichiometric and the oxidation by-product isocyanuric acid can be easily isolated and recovered. Besides of arylboronic acids, aryl trifluoroborates and aryl trihydroxyborates salts are also able to perform this transformation. (Figure presented.).
- Sun, Nan,Zheng, Kai,Sun, Pengyuan,Chen, Yang,Jin, Liqun,Hu, Baoxiang,Shen, Zhenlu,Hu, Xinquan
-
p. 3577 - 3584
(2021/06/15)
-
- O-(tert-butyl) Se-phenyl selenocarbonate: A convenient, bench-stable and metal-free precursor of benzeneselenol
-
A study by our laboratory shows that air, light and moisture stable O-(tert-butyl) Se-phenyl selenocarbonate could be employed as a safer, practical and efficient alternative to generate “in situ” benzeneselenol or benzeneselenolate anion under different and transition metal-free conditions. This procedure seems to be of general application since the nucleophilic selenium species obtained can be trapped by electrophiles such as alkyl halides, epoxides and electron-deficient alkenes and alkynes under different reaction conditions.
- Temperini, Andrea,Siciliano, Carlo
-
-
- Metal-Free Synthesis of Unsymmetrical Aryl Selenides and Tellurides via Visible Light-Driven Activation of Arylazo Sulfones
-
A protocol for the visible light driven preparation of unsymmetrical (hetero)aryl selenides and tellurides is described herein. The method exploits the peculiar photoreactivity of arylazo sulfones that act as thermally stable, precursors of aryl radicals under both photocatalyst- and additive-free conditions. The method developed shows an impressive versatility (more than fifty compounds isolated).
- Fagnoni, Maurizio,Li, Ankun,Li, Yuxuan,Liu, Junjie,Lu, Kui,Protti, Stefano,Shan, Xiwen,Tian, Miaomiao,Zhao, Xia
-
p. 7358 - 7367
(2020/12/01)
-
- Dechalcogenization of Aryl Dichalcogenides to Synthesize Aryl Chalcogenides via Copper Catalysis
-
An application for dechalcogenization of aryl dichalcogenides via copper catalysis to synthesize aryl chalcogenides is disclosed. This approach is highlighted by the practical conditions, broad substrate scope, and good functional group tolerance with several sensitive groups such as aldehyde, ketone, ester, amide, cyanide, alkene, nitro, and methylsulfonyl. Furthermore, the robustness of this methodology is depicted by the late-stage modification of estrone and synthesis of vortioxetine. Remarkably, synthesis of more challenging organic materials with large ring tension under milder conditions and synthesis of some halogen contained diaryl sulfides which could not be synthesized using metal-catalyzed coupling reactions of aryl halogen are successfully accomplished with this protocol.
- Cao, Fei,Chen, Jinhong,Deng, Jiedan,Deng, Xuemei,Hou, Yongsheng,Shao, Xiangfeng,Shi, Tao,Wang, Yongqiang,Wang, Zhen,Wu, Lingxi,Yang, Jinru,Yang, Yuhang
-
p. 2707 - 2712
(2020/03/11)
-
- New arylselanylpyrazole-copper catalysts: Highly efficient catalytic system for C–Se and C–S coupling reactions
-
We describe herein the use of arylselanylpyrazole–copper complexes as versatile catalysts for C–Se and C–S coupling reactions. The performance of these complexes for C–Se reactions was investigated in chalcogenoacetylene synthesis. The reactions were carried out under mild and aerobic conditions and afforded selanylalkynes bearing a variety of electron-withdrawing and electron-donating groups. The performance of these catalysts for C–S coupling was investigated through the reaction of aryl halides with thiols and products were obtained in moderate to excellent yields. A plausible mechanism for selenoacetylene synthesis is also suggested, and the 77Se NMR results show that these arylselanylpyrazole ligands act as hemilabile ligands. High-resolution mass spectrometry was used to investigate the intermediates and also to corroborate the proposed catalytic cycle.
- Coelho, Felipe Lange,Dresch, Lucielle Codeim,Stieler, Rafael,Campo, Leandra Franciscato,Schneider, Paulo Henrique
-
-
- Transition-Metal-Free Aryl-Heteroatom Bond Formation via C-S Bond Cleavage
-
Aryl-heteroatom bonds (C-Het) are almost ubiquitously present in chemical molecules. However, methods for diverse C-Het bond formations from a simple substrate are limited. Herein, we report a convenient and efficient C-S bond transformation of aryl sulfoniums to various C-Het bonds (C-O, C-S, C-Sn, C-Si, C-Se) in the absence of any transition-metal catalyst. These reactions proceeded in mild conditions with a wide substrate scope.
- Zhao, Jian-Nan,Kayumov, Muzaffar,Wang, Dong-Yu,Zhang, Ao
-
p. 7303 - 7306
(2019/10/02)
-
- Cu-Mediated arylselenylation of aryl halides with trifluoromethyl aryl selenonium ylides
-
An unprecedented arylselenylation of aryl halides with trifluoromethyl aryl selenonium ylides in the presence of copper is described. The reaction proceeded at 100-140 °C under ligand- and additive-free conditions for 3-20 h to form a variety of unsymmetrical diaryl selenides in good to high yields. Arylselenylation is easy to operate, has good functional group tolerance, and demonstrates the different reaction profiles of trifluoromethyl aryl selenonium ylides from the homologous trifluoromethyl aryl sulfonium ylides.
- Wu, Shuai,Shi, Jin,Zhang, Cheng-Pan
-
p. 7468 - 7473
(2019/08/20)
-
- New routes for the synthesis of unsymmetrical diarylselenides: Effect of heat, light and ultrasound
-
Herein, we report the photochemical coupling of diphenyldiselenides with substituted phenylhydrazine hydrochloride without catalyst. The protocol was developed not only in presence of sunlight and UV light but also under thermal condition for comparison study. Moreover, ultrasound assisted new catalytic protocol was developed using Ni(II)/L-proline system in DMSO with the advantage of shorter reaction time compared to earlier reports. We have also developed a new C-Se cross coupling reaction where phenylselenyl chloride and arylhydrazine hydrochlorides were effectively coupled using developed catalytic system.
- Sahani, Amber J.,Burange, Anand S.,Thakur, Seema D.,Jayaram, Radha V.
-
-
- Syntheses of Thioethers and Selenide Ethers from Anilines
-
In this study, a general procedure was proposed for synthesizing thioethers and selenide ethers from anilines under solvent-free and transition-metal-free conditions. Thioethers were formed when anilines reacted with thiols under blue light-emitting-diode (LED) irradiation at room temperature without a photocatalyst. When reactions were performed using anilines and diselenides, the corresponding selenide ethers were obtained with satisfactory to excellent yields. The reaction was performed under photocatalyst-free and solvent-free conditions without blue LEDs. The advantages of this system include convenient operations, mild reaction conditions, satisfactory functional group tolerance, and late-stage selenylation of drug molecules.
- Shieh, Yi-Chen,Du, Kai,Basha, R. Sidick,Xue, Yung-Jing,Shih, Bo-Hao,Li, Liang,Lee, Chin-Fa
-
p. 6223 - 6231
(2019/05/24)
-
- Nickel(II) Tetraphenylporphyrin as an Efficient Photocatalyst Featuring Visible Light Promoted Dual Redox Activities
-
Nickel(II) tetraphenylporphyrin (NiTPP) is presented as a robust, cost-effective and efficient visible light induced photoredox catalyst. The ground state electrochemical data (CV) and electronic absorption (UV-Vis) spectra reveal the excited state redox potentials for [NiTPP]*/[NiTPP].? and NiTPP].+/[NiTPP]* couples as +1.17 V and ?1.57 V vs SCE respectively. The potential values represent NiTPP as a more potent photocatalyst compare to the well-explored [Ru(bpy)3]2+. The non-precious photocatalyst exhibits excited state redox reactions in dual fashions, i. e., it is capable of undergoing both oxidative as well as reductive quenching pathways. Such versatility of a photocatalyst based on first-row transition metals is very scarce. This unique phenomenon allows one to perform diverse types of redox reactions by employing a single catalyst. Two different sets of chemical reactions have been performed to represent the synthetic utility. The catalyst showed superior efficiency in both carbon-carbon and carbon-heteroatom bond-forming reactions. Thus, we believe that NiTPP is a valuable addition to the photocatalyst library and this study will lead to more practical synthetic applications of earth-abundant-metal-based photoredox catalysts. (Figure presented.).
- Mandal, Tanumoy,Das, Sanju,De Sarkar, Suman
-
supporting information
p. 3200 - 3209
(2019/05/16)
-
- Efficient heterogeneous copper-catalysed C–Se coupling of aryl iodides with symmetrical diselenides towards unsymmetrical monoselenides
-
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
-
p. 584 - 588
(2018/11/27)
-
- C-Se cross-coupling of arylboronic acids and diphenyldiselenides over non precious transition metal (Fe, Cu and Ni) complexes
-
Various tetradentate and tridentate ligands such as salophane, bishydrazone, bisbenzimidazolyl pyridine and isonicotinohydrazide have been prepared. Transition metal complexes of these ligands with Cu, Ni and Fe have been further synthesized and characterized by UV–vis, IR, NMR and CHN analysis. Catalytic activity of the metal complexes was tested for the cross coupling of diarylchalcogenide with arylboronic acid in DMSO as solvent in presence of a base. These non-precious metal complexes catalysed cross coupling reactions smoothly in shorter reaction time compared to earlier reports with comparable yields.
- Sahani, Amber J.,Jayaram, Radha V.,Burange, Anand S.
-
-
- Merging visible-light photoredox and micellar catalysis: Arylation reactions with anilines nitrosated in situ
-
An aqueous photocatalytic system was designed by merging visible-light photoredox catalysis with micellar catalysis. Eosin B, an organic dye, was utilized as the photocatalyst, and Triton X-100 was employed as the surfactant; both are inexpensive and commercially available. This clean and energy-saving catalytic system enables photocatalytic reactions of the diazonium ion generated in situ to proceed smoothly in water without any co-solvents or additives at room temperature.
- Bu, Mei-Jie,Lu, Guo-Ping,Jiang, Jianzhong,Cai, Chun
-
p. 3728 - 3732
(2018/08/12)
-
- Metal-free synthesis of unsymmetrical organoselenides and selenoglycosides
-
A one-pot, metal-free procedure has been developed to synthesize unsymmetrical organoselenides. In the first step of the reaction, arylation of potassium selenocyanate (KSeCN) with an iodonium reagent proceeds in the absence of a metal catalyst to produce
- Guan, Yong,Townsend, Steven D.
-
p. 5252 - 5255
(2017/11/06)
-
- Iron(0) nanoparticles mediated direct conversion of aryl/heteroaryl amines to chalcogenides via in situ diazotization
-
A simple procedure for the synthesis of organo-chalcogenides has been developed by the reaction of aryl/heteroaryl amines with di-aryl/heteroaryl dichalcogenides in the presence of tBuONO and Fe(0) nanoparticles. The reaction proceeds via in situ diazotization followed by chalcogenation. A series of functionalized diaryl/aryl heteroaryl/diheteroaryl/aryl-alkyl selenides, sulfides and tellurides have been obtained by this procedure. Significantly, using this procedure 2,4-dinitroaniline is converted to (2,4-dinitrophenyl)(phenyl)selane which is known as thioredoxin reductase (TR) and glutathione reductase (GR) inhibitor. The reaction goes by a radical pathway and a plausible mechanism has been suggested.
- Panja, Subir,Maity, Pintu,Kundu, Debasish,Ranu, Brindaban C.
-
supporting information
p. 3441 - 3445
(2017/08/10)
-
- A Highly Efficient Copper-Catalyzed Synthesis of Unsymmetrical Diaryl- and Aryl Alkyl Chalcogenides from Aryl Iodides and Diorganyl Disulfides and Diselenides
-
An efficient and convenient protocol has been developed for the copper-catalyzed reaction of aryl iodides and diorganyl disulfides and diselenides. A variety of symmetrical and unsymmetrical diaryl- and aryl alkyl chalcogenides were synthesized with good functional group tolerance and chemoselectivity by using copper(I) iodide as a catalyst, 4′-(4-methoxyphenyl)-2,2′:6′,2′′-terpyridine as ligand, and KOH as base under an inert atmosphere.
- Movassagh, Barahman,Hosseinzadeh, Zhila
-
supporting information
p. 777 - 781
(2016/03/12)
-
- Development of a selenide-based fluorescent probe for imaging hypochlorous acid in lysosomes
-
The development of fluorescent probes for hypochlorous acid (HOCl) has received intense attention because of the biological significance of HOCl. In this work, a novel fluorescent probe based on a selenide switch for the detection of HOCl in lysosomes has been designed and synthesized on a 1,8-naphthalimide scaffold. The probe exhibited a high selectivity for HOCl over various reactive oxygen species (ROS) with a fast response and a large fluorescence enhancement in aqueous media. Confocal microscopy imaging of living cells indicated that the probe was able to accumulate in lysosomes and was successfully applied to imaging exogenous HOCl in living cells. Attempts of using Lyso-NI-Se to image HOCl in stimulated RAW264.7 cells failed, probably due to the absence of endogenous HOCl in lysosomes or the undesirable detection limit.
- Qu, Zongjin,Ding, Junxia,Zhao, Meiyu,Li, Peng
-
-
- Ascorbic Acid Promoted Metal-Free Synthesis of Aryl Sulfides with Anilines Nitrosated in Situ by tert -Butyl Nitrite
-
A mild, metal-free synthesis of aryl sulfides has been disclosed. Aryl diazonium ion was generated by the in situ nitrosation of aniline, and it was reduced by ascorbic acid (vitamin C) to form aryl radical, which underwent a thiolation with disulfide to yield aryl sulfide. The reaction proceeded smoothly without heating or irradiation. This strategy was also expanded to the synthesis of aryl selenides.
- Bu, Mei-Jie,Lu, Guo-Ping,Cai, Chun
-
supporting information
p. 1841 - 1846
(2015/08/06)
-
- Visible light photocatalyzed direct conversion of aryl-/heteroarylamines to selenides at room temperature
-
A novel strategy for the direct conversion of aryl- and heteroarylamines to selenides has been developed via diazotization of amines with tert-butyl nitrite in neutral medium followed by reaction with diaryl/diheteroaryl/dialkyl diselenides in one pot under photocatalysis at room temperature in the absence of any metal. This reaction is also applied for the synthesis of tellurides. The selenylation of heteroarylamine by this protocol is of much significance because of the difficulty in diazotization of these molecules by a standard diazotization method in acid medium.
- Kundu, Debasish,Ahammed, Sabir,Ranu, Brindaban C.
-
supporting information
p. 1814 - 1817
(2014/04/17)
-
- Solvent-controlled halo-selective selenylation of aryl halides catalyzed by Cu(II) supported on Al2O3. A general protocol for the synthesis of unsymmetrical organo mono- and bis-selenides
-
Alumina-supported Cu(II) efficiently catalyzes selenylation of aryl iodides and aryl bromides by diaryl, dialkyl, and diheteroaryl diselenides in water and PEG-600, respectively, leading to a general route toward synthesis of unsymmetrical diaryl, aryl-alkyl, aryl-heteroaryl, and diheteroaryl selenides. A sequential reaction of bromoiodobenzene with one diaryl/diheteroaryl/dialkyl diselenide in water and another diaryl/diheteroaryl/dialkyl diselenide in PEG-600 in the second step produces unsymmetrical diaryl, diheteroaryl, or aryl-alkyl bis-selanyl benzene. A library of functionalized organo mono- and bis-selenides, including a potent biologically active molecule and a couple of analogues of bioactive selenides, were obtained in high yields by this protocol. The reactions are chemoselective and high yielding. The Cu-Al2O 3 catalyst is recycled for seven runs without any appreciable loss of activity.
- Chatterjee, Tanmay,Ranu, Brindaban C.
-
p. 7145 - 7153
(2013/08/23)
-
- Potassium tert-butoxide-mediated synthesis of unsymmetrical diaryl ethers, sulfides and selenides from aryl bromides
-
Potassium tert-butoxide mediated carbon-chalcogen C-E (E=O, S and Se) coupling reaction has been studied from aryl bromide and phenol/aryl disulfide/diselenide substrates. A series of unsymmetrical diaryl chalcogenides were accessed from aryl bromide and diaryl dichalcogenide precursors by using 2.5 equiv of potassium tert-butoxide in DMSO at 80 C. Unsymmetrical diaryl ethers were also obtained by using phenol precursors at 40-45 C. Aryl bromides with methyl, trifluoromethyl, methoxy and nitro substituents showed compatibility in the carbon-chalcogen bond forming reaction. 4-Methoxy, methyl, trifluoromethyl substituted bromobenzene substrates gave two regioisomers: 3-substituted and 4-substituted diaryl chalcogenides when reacted with phenols/diaryl disulfides/diselenides. Formation of two regioisomeric diaryl chalcogenides in the reaction mixture suggests that potassium tert-butoxide reacts with bromobenzene to produce benzyne intermediate, which subsequently reacts with diaryl dichalcogenides and finally give a regioisomeric mixture of 4-substituted and 3-substituted diaryl chalcogenides.
- Kumar, Amit,Bhakuni, Bhagat Singh,Prasad, Ch. Durga,Kumar, Shailesh,Kumar, Sangit
-
p. 5383 - 5392
(2013/07/04)
-
- Palladium-catalyzed cross-coupling of PhSeSnBu3 with aryl and alkyl halides in ionic liquids: A practical synthetic method of diorganyl selenides
-
Palladium-catalyzed cross-coupling reactions of phenyl tributylstannyl selenide with aryl and alkyl halides can proceed smoothly in room temperature ionic liquid, 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF 6]), to give the corresponding diorganyl selenides in good to high yields. The coupling reaction run in [bmim][PF6] has the advantages of rate acceleration and increase of yield in contrast to the reaction run in toluene. Our system not only avoids the use of easily volatile toluene as a solvent but also solves the basic problem of palladium catalyst reuse.
- Zhao, Hong,Hao, Wenyan,Xi, Zhiwen,Cai, Mingzhong
-
experimental part
p. 2661 - 2665
(2012/01/04)
-
- A near-IR reversible fluorescent probe modulated by selenium for monitoring peroxynitrite and imaging in living cells
-
We have developed a near-IR reversible fluorescent probe containing an organoselenium functional group that can be used for the highly sensitive and selective monitoring of peroxynitrite oxidation and reduction events under physiological conditions. The probe effectively avoids the influence of autofluorescence in biological systems and gave positive results when tested in both aqueous solution and living cells. Real-time images of cellular peroxynitrite were successfully acquired.
- Yu, Fabiao,Li, Peng,Li, Guangyue,Zhao, Guangjiu,Chu, Tianshu,Han, Keli
-
p. 11030 - 11033
(2011/09/14)
-
- An efficient copper(I) iodide catalyzed synthesis of diaryl selenides through Cse bond formation using solvent acetonitrile as ligand
-
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
-
experimental part
p. 2297 - 2302
(2011/09/16)
-
- Synthesis of azido arylselenides and azido aryldiselenides: a new class of selenium-nitrogen compounds
-
We present here our results of the efficient synthesis of azido arylselenides and azido aryldiselenides under mild conditions. Starting from nitrogen-substituted benzenes, we incorporated selenium atom at aromatic ring and obtained amino arylselenides and diselenides in satisfactory yields. Treatment of these compounds with iso-pentyl nitrite (i-C5H11ONO) and azido trimethylsilane (Me3SiN3) in THF affords a variety of azido arylselenides and diselenides in good to excellent yields.
- Deobald, Anna Maria,Simon de Camargo, Leandro R.,Tabarelli, Greice,H?rner, Manfredo,Rodrigues, Oscar E.D.,Alves, Diego,Braga, Ant?nio L.
-
experimental part
p. 3364 - 3367
(2010/08/19)
-
- Copper nano-catalyst: Sustainable phenyl-selenylation of aryl iodides and vinyl bromides in water under ligand free conditions
-
A simple and efficient procedure for the synthesis of aryl- and vinyl-selenides has been developed by a copper nanoparticle catalysed reaction of aryl iodide/vinyl bromide with diphenyl diselenide in the presence of zinc in water. (E)-Vinyl bromides produce (E)-vinyl selenides stereoselectively, whereas (Z)-vinyl bromides provide mixtures of (E) and (Z) isomers. The catalyst was recycled.
- Saha, Amit,Saha, Debasree,Ranu, Brindaban C.
-
experimental part
p. 1652 - 1657
(2009/06/28)
-
- CsOH·H2O promoted areneselenenylation of aryl bromides and iodides
-
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.
-
p. 140 - 141
(2007/10/03)
-
- Palladium-catalyzed phenyl-selenylation with n-Bu3SnSePh in one-pot two-step reactions
-
We have studied the Pd-catalyzed cross-coupling reaction of a stannane derived from selenium n-Bu3SnSePh (1) with aryl and perfluoroalkyl iodides. Herein a very efficient one-pot two-step selenylation reaction to form a C-Se bond is reported. Ph2Se2 reacts with Na metal in liquid ammonia yielding PhSe- ions. To this solution n-Bu3SnCl was added to afford 1, which was introduced in the palladium-catalyzed coupling reaction without isolation. These reactions afford functionalized diarylselenides and phenylperfluroalkyl selenides from good to high yields (38-98%).
- Bonaterra, Mariana,Martín, Sandra E.,Rossi, Roberto A.
-
p. 3511 - 3515
(2007/10/03)
-
- Magnesium-Induced Copper-Catalyzed Synthesis of Unsymmetrical Diaryl Chalcogenide Compounds from Aryl Iodide via Cleavage of the Se-Se or S-S Bond
-
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
-
p. 915 - 920
(2007/10/03)
-
- Copper-catalyzed synthesis of diaryl selenide from aryl iodide and diphenyl diselenide using magnesium metal
-
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
-
p. 829 - 832
(2007/10/03)
-
- Structural studies on diaryl selenide dihalides in solution: Molecular complex formation of substituted diphenyl selenides with bromine
-
Diaryl selenides that yield molecular complexes (MC) with bromine are prepared by modulating the effective electronegativity of the selenium atom and the steric environment around the atom in diphenyl selenide (1) with various substituents at the 2-, 3- and/or 4-positions. Halogen induced 1H and 13C NMR chemical shifts of the diaryl selenides are examined. The chlorine and iodine adducts of the selenides are shown to be trigonal bipyramidal adducts (TB) and MC, respectively. In the case of bromine adducts, the structures of (3- and 4-YC6H4)2SeBr2 are demonstrated to be MC if Y is CN and NO2, contrary to the general rule: they are TB if Y is less electron-withdrawing than the ethoxycarbonyl group. The CN and NO2 groups increase the effective electronegativity of the Se atom in (3- and 4-YC6H4)2Se and do not give TB with bromine. The four chloro groups at all meta-positions in 1 are also effective for MC formation. However, 3,5-(O2N)2C6H3SeBr2Ph is TB. Ab initio MO calculations show that the structures of (3-O2NC6H4)2Se and 3,5-(O2N)2C6H3SePh are close to the C2 and C s symmetries, respectively, which reveals that the conformational change is also important when the structures of the bromine adducts are determined. The steric congestion must be more severe for TB formation than for MC formation. The structures of 2,6-Cl2C6H3- SeBr2C6H4Y-p (Y = H and Br) are MC, which shows that the steric effect of 2,6-Cl2C6H3 group is effective for MC formation. (2-MeC6H4)2SeBr2 and (2-ClC6H4)2SeBr2 are TB and MC, respectively: the electronic effect of the Cl group must play an additional role in the MC formation since the bulkiness of the Me and Cl groups are expected to be similar. The bromine adduct of (2,4,6-Me3C6H2)2Se is also concluded to be MC: the steric effect of the four Me groups at the ortho-positions is large enough to give MC with bromine. The oxidation potentials (Eox) of the diaryl selenides explain well the structures of the bromine adducts: the electronic effect is directly correlated with Eox and the importance of the steric effect has been brought into sharp relief by Eox. Results of MO calculations support the outline of the observations. The structural behavior of some halogen adducts such as 2,6-Cl2C6H3SeCl2C6H 4Y-p (TB: Y = H and Br) is also discussed in some detail.
- Nakanishi, Waro?,Hayashi, Satoko,Kusuyama, Yoshiaki
-
p. 262 - 270
(2007/10/03)
-
- Tributyltin aryl selenides as efficient arylselenating agents. Synthesis of diaryl and aryl organyl selenides
-
Tributyltin aryl selenides are highly efficient arylselenating agents in reactions with aryl iodides and aryl triflates under catalysis with Pd and Ni complexes respectively. They also may be used as efficient source of active arylselenolate anion in the
- Beletskaya,Sigeev,Peregudov,Petrovskii
-
p. 1463 - 1475
(2007/10/03)
-
- New approaches to the synthesis of unsymmetrical diaryl selenides
-
Unsymmetrical diaryl selenides PhSeAr were obtained by the palladium catalysed reactions of aryl (heteroaryl) iodide or triflate with Bu3SnSePh in high yields. The same compounds can be obtained by the non-catalytic reactions of Bu3SnSePh with ArN2BF4 or (ArN2)2ZnCl4.
- Beletskaya, Irina P.,Sigeev, Alexander S.,Peregudov, Alexander S.,Petrovskii, Pavel V.
-
-
- New synthetic method of diorganyl selenides: Palladium-catalyzed reaction of PhSeSnBu3 with aryl and alkyl halides
-
(formula presented) Palladium complexes such as Pd(PPh3)4 catalyzed the reaction of phenyl tributylstannyl selenide (PhSeSnBu3) with aryl and alkyl halides, giving the corresponding diaryl and alkylaryl selenides in moderate to good yields.
- Nishiyama, Yutaka,Tokunaga, Keiji,Sonoda, Noboru
-
p. 1725 - 1727
(2008/02/11)
-
- Structural Study of Aryl Selenides in Solution Based on 77Se NMR Chemical Shifts: Application of the GIAO Magnetic Shielding Tensor of the 77Se Nucleus
-
The 77Se NMR chemical shifts (δobsd(Se)) of p-YC6H4SeMe (1: Y = H (a), OMe (b), Me (c), Cl (d), Br (e), COOR (f), and NO2 (g)) and p-YC6H4SePh (2) were determined or redetermined
- Nakanishi, Waro,Hayashi, Satoko
-
p. 6074 - 6081
(2007/10/03)
-
- Rapid and precise preparation of reactive benzeneselenolate solutions by reduction of diphenyl diselenide with hydrazine-sodium methanolate
-
Solutions of sodium benzeneselenolate sufficiently reactive to effect 'aromatic substitution and ester dealkylation are prepared in DMSO or NMP from diphenyl diselenide and hydrazine hydrate by titration with methanolic sodium methanolate.
- Henriksen, Lars,Stuhr-Hansen, Nicolai
-
p. 1915 - 1916
(2007/10/03)
-
- Thiol/Diselenide Exchange for the Generation of Benzeneselenolate Ion. Catalytic Reductive Ring-Opening of α,β-Epoxy Ketones
-
In the presence of N-acetylcysteine sodium salt, benzeneselenolate ion was generated in situ from diphenyl diselenide via thiol/diselenide and thiol/selenenyl sulfide exchange in aqueous methanol under mild conditions.Benzeneselenolate ion thus formed was efficiently alkylated and arylated to afford alkyl phenyl selenides and aryl phenyl selenides, respectively. α,β-Epoxy ketones were catalytically reduced by benzeneselenolate ion to afford β-hydroxy ketones (aldols) in good yields.The stereospecificity of the reaction was demonstrated in the preparation of optically active β-hydroxy ketones from chiral α,β-epoxy ketones.
- Engman, Lars,Stern, David
-
p. 5179 - 5183
(2007/10/02)
-
- The use of aminoiminomethanesulfinic acid (thiourea dioxide) under phase transfer conditions for generating organochalcogenate anions. Synthesis of sulfides, selenides and tellurides
-
A procedure is described which allows for the in situ synthesis of arylalkyl, diaryl and dialkylchalcogenides under phase transfer conditions starting from the corresponding diorganodichalcogenides.The dichalcogenides are reduced by aminoiminomethanesulfinic acid (thiourea dioxide) in alkaline medium and catalyzed by a quaternary ammonium salt.The reduction proceeds easily for diaryl disulfides and diaryl diselenides at a sodium hydroxide concentration of 13percent; diaryl ditellurides require a 50percent sodium hydroxide solution to give the aryl tellurolate anion.The dialkyl diselenides and dialkyl ditellurides are more difficult to reduce.The intermediate arylthiolates and arylselenolates are quenched by alkyl and activated aryl halides to give the corresponding sulfides and selenides in high yield (77-97percent).The aryltellurolates react with alkyl halides giving the aryl alkyl tellurides in 81-96percent yield.The procedure could not be successfully used for the synthesis of dialkylselenides and dialkyl tellurides; low yields and mixture of products were formed.
- Comasseto, J. V.,Lang, E. S.,Ferreira, J. Tercio B.,Simonelli, F.,Correira, V. R.
-
p. 329 - 340
(2007/10/02)
-
- SYNTHESIS OF DIARYLSELENIDES AND DIARYLSULFIDES UNDER PHASE TRANSFER CONDITIONS
-
Diarylselenides and diarylsulfides are synthesized from the corresponding diaryldiselenide and diaryldisulfide by reduction with aminoiminomehanesulfinic acid, and reaction with activated aryl halides under phase transfer conditions.The reactions yields vary from good to excellent.
- Ferreira, J. Tercio,Simonelli, F.,Comasseto, J. V.
-
p. 1335 - 1342
(2007/10/02)
-
- Aryl Arylazo Sulfones Chemistry. 2. Reactivity toward Alkaline Alkane- and Areneselenolate and Alkane- and Arenetellurolate Anions
-
Tolyl arylazo sulfones react with various alkyl- and arylseleno reagents to produce substituted alkyl aryl and unsymmetrical diaryl selenides.The corresponding tellurides can also be obtained.Isolated yields in both cases are good.This procedure is an interesting alternative to the classical Sandmeyer reaction.
- Evers, Michel J.,Christiaens, Leon E.,Renson, Marcel J.
-
p. 5196 - 5198
(2007/10/02)
-
- Oxidation of Hydrazines with Benzeneseleninic Acid and Anhydride
-
Benzeneseleninic acid (1) and anhydride (2) oxidize hydrazine or 1,2-disubstituted derivatives to corresponding diazenes.Hydrazides afford selenoesters 4, N,N'-diacyl- or diaroylhydrazines 5, and carboxylic acids.Benzeneselenenic acid (7) is a required intermediate in selenoester formation and may be generated independently by the reaction of triphenylphosphine with 1.Selenoesters are efficiently prepared by the slow addition of a mixture of the hydrazide and triphenylphosphine to 1 in dichloromethane solution.Polar solvents are unsuitable.Inverse addition provides compounds 5 as major products.Oxidation of hydrazides of structure HO-(CH2)nCONHNH2 gives the corresponding selenoesters 14 and acids 16 when n=11 or 14 lactones 17 and 18 when n=4 or 3.Arylhydrazines react with 1 or 2 to furnish arenes 23 and aryl phenyl selenides 24.
- Back, Thomas G.,Collins, Scott,Ker, Russell G.
-
p. 1564 - 1570
(2007/10/02)
-
- Oxidation of Ketone and Aldehyde Hydrazones, Oximes, and Semicarbazones and of Hydroxylamines and Hydrazo-compounds, using Benzeneselenic Anhydride
-
Benzeneseleninic anhydride (1; BSA) is an effective reagent for the mild regeneration of the carbonyl group from ketone phenylhydrazones, p-nitrophenylhydrazones, tosylhydrazones, oximes, and semicarbazones at 40-50 deg C.Tosylhydrazones and oximes of aldehydes are also readily converted into the parent aldehyde.The phenylhydrazone and p-nitrophenylhydrazone derivatives of aldehydes afford ketoazo-compounds.The ketoazo-species could also be prepared by oxidation of the corresponding hydrazide with compound (1).Both aromatic and aliphatic hydrazo-compounds and hydroxylamines can be oxidised to azo- and nitrozo-derivatives respectively.
- Barton, Derek H. R.,Lester, David J.,Ley, Steven V.
-
p. 1212 - 1217
(2007/10/02)
-