- A highly efficient heterogeneous ruthenium(III)-catalyzed reaction of diaryl diselenides with alkyl halides leading to unsymmetrical diorganyl selenides
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A highly efficient heterogeneous ruthenium(III)-catalyzed reaction of diaryl diselenides with alkyl halides was achieved in DMF at 100?°C in the presence of 2?mol% of an MCM-41-immobilized bidentate nitrogen ruthenium(III) complex [MCM-41-2N-RuCl3] and zinc, yielding a variety of unsymmetrical diorganyl selenides in good to excellent yields. This new heterogeneous ruthenium catalyst can easily be prepared via a simple two-step procedure from commercially readily available and inexpensive reagents, and recovered by filtration of the reaction solution and recycled for at least eight times without a significant loss of activity.
- Chen, Qiurong,Wang, Pingping,Yan, Tao,Cai, Mingzhong
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- Reductive coupling of disulfides and diselenides with alkyl halides catalysed by a silica-supported phosphine rhodium complex using hydrogen as a reducing agent
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The reductive coupling of disulfides and diselenides with alkyl halides was achieved in THF at 65 °C in the presence of 3 mol% of a silica-supported phosphine rhodium complex and triethylamine using hydrogen as a reducing agent, affording a variety of unsymmetrical sulfides and selenides in high yields. The heterogeneous rhodium catalyst can be recovered by a simple filtration and reused several times without significant loss of activity. Reaction with an acyl halide was also observed.
- Zhang, Hean,Hu, Mangen,Cai, Mingzhong
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p. 645 - 647
(2013/11/06)
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- Magnetically separable and reusable copper ferrite nanoparticles for cross-coupling of aryl halides with diphenyl diselenide
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A simple and efficient procedure for the synthesis of diaryl selenides has been developed by a copper ferrite nanoparticle catalyzed reaction of aryl iodides/aryl bromides with diphenyl diselenide in the presence of base and solvent at 120 °C. Using this protocol, a variety of diselenides were obtained in good to excellent yields. The copper ferrite nanoparticles were magnetically separated, recycled, and reused up to three cycles. Copyright
- Swapna, Kokkirala,Murthy, Sabbavarapu Narayana,Nageswar, Yadavalli Venkata Durga
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experimental part
p. 1940 - 1946
(2011/04/27)
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- Bimetallic system for the synthesis of diorganyl selenides and sulfides, chiral β-seleno amines, and seleno- and thioesters
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The bimetallic reagent Sn(II)/Cu(II) in [bmim]BF4 was efficiently used for the cleavage of diaryl diselenides and disulfides and reacts with a variety of organic substrates, such as organic halides, acid chlorides, and β-amino mesylates affording the diorganyl selenides and sulfides within very short reaction times, under mild conditions and with excellent yields, using BMIM-BF4 as a reusable solvent.
- Gul, Kashif,Narayanaperumal, Senthil,Dornelles, Luciano,Rodrigues, Oscar E.D.,Braga, Antonio Luiz
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supporting information; experimental part
p. 3592 - 3596
(2011/07/31)
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- Indium-mediated cleavage of diphenyl diselenide and diphenyl disulfide: efficient one-pot synthesis of unsymmetrical diorganyl selenides, sulfides, and selenoesters
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A convenient and efficient method was developed for the synthesis of alkyl phenyl selenides, sulfides, and selenoesters in one-pot reaction by using indium metal. The reaction showed the selectivity for tert-alkyl, benzylic, and allylic halides over primary and secondary alkyl halides. For the reaction of primary and secondary alkyl iodides and bromides, the yields of selenides were improved by the addition of a catalytic amount of iodine.
- Munbunjong, Wanida,Lee, Eun Hwa,Ngernmaneerat, Poonlarp,Kim, Sung Jun,Singh, Gurpinder,Chavasiri, Warinthorn,Jang, Doo Ok
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body text
p. 2467 - 2471
(2009/08/15)
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- Eco-friendly cross-coupling of diaryl diselenides with aryl and alkyl bromides catalyzed by CuO nanopowder in ionic liquid
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An eco-friendly cross-coupling reaction of aryl and alkyl bromides with diselenides using a catalytic amount of CuO nanopowder as a catalyst and an ionic liquid as a recyclable solvent is reported. The system shows high efficiency to catalyze this transformation, and in a green fashion due to the recyclable approach and the non-residual design protocol. This procedure has been utilized for the synthesis of a variety of diaryl selenides in good to excellent yields from the readily available aryl and alkyl bromides and diselenides. The Royal Society of Chemistry 2009.
- Singh, Devender,Alberto, Eduardo E.,Rodrigues, Oscar Endrigo Dorneles,Braga, Antonio Luiz
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experimental part
p. 1521 - 1524
(2010/06/13)
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- Efficient synthesis of diorganyl selenides via cleavage of Se-Se bond of diselenides by indium(III) catalyst and zinc
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A simple and efficient procedure for the synthesis of unsymmetrical diorganyl selenides from an one-pot indium(III) catalyzed procedure, in the presence of zinc, has been developed. Various organic halides and even the unreactive organic chlorides underwe
- Braga, Antonio L.,Schneider, Paulo H.,Paix?o, Marcio W.,Deobald, Anna M.
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p. 7195 - 7198
(2007/10/03)
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- Ruthenium(III) chloride catalyzed efficient synthesis of unsymmetrical diorganyl selenides via cleavage of dibenzyl and diphenyl diselenides in the presence of zinc
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An efficient one-pot route to unsymmetrical diorganyl selenides has been developed by ruthenium-(III) chloride catalyzed reactions of dibenzyl or diphenyl diselenides with alkyl halides in the presence of zinc. Organic iodides, bromides, and activated chlorides underwent the reactions efficiently. Unreactive organic chlorides also underwent the same type of selenation with sodium bromide as the additive.
- Zhao, Xiaodan,Yu, Zhengkun,Yan, Shenggang,Wu, Sizhong,Liu, Ren,He, Wei,Wang, Liandi
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p. 7338 - 7341
(2007/10/03)
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- Rhodium-catalyzed reductive coupling of disulfides and diselenides with alkyl halides, using hydrogen as a reducing agent
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(Chemical Equation Presented) We have established that RhCl(PPh 3)3 catalyzes a reductive coupling of disulfides and diselenides with alkyl halides in the presence of triethylamine using hydrogen as a reducing agent. This reaction serves as a convenient new method to produce unsymmetrical sulfides and selenides from disulfides and diselenides instead of unstable and odoriferous thiols and selenols.
- Ajiki, Kaori,Hirano, Masao,Tanaka, Ken
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p. 4193 - 4195
(2007/10/03)
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- A novel and highly efficient synthetic route to unsymmetrical organoselenides using cesium bases
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A new and convenient one-pot method for the preparation of unsymmetrical selenides has been developed. In the presence of cesium hydroxide, molecular sieves, and DMF, benzeneselenol undergoes direct alkylation with various alkyl halides for the synthesis of alkyl phenyl selenides in moderate to excellent yields. Another method to prepare unsymmetrical organoselenides was also completed by coupling terminal alkynes with benzeneselenyl bromide. As an application, the synthesis of a selenopeptide was also accomplished. Furthermore, this methodology was extended to the synthesis of an organoselenide on solid support.
- Cohen, Richard J.,Fox, Daniel L.,Salvatore, Ralph Nicholas
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p. 4265 - 4268
(2007/10/03)
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- Indium(I) iodide-promoted cleavage of diaryl diselenides and disulfides and subsequent condensation with alkyl or acyl halides. One-pot efficient synthesis of diorganyl selenides, sulfides, selenoesters, and thioesters
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Diphenyl diselenides and disulfides undergo facile cleavages by indium(I) iodide and the corresponding generated selenate and thiolate anions condense in situ with alkyl or acyl halides present in the reaction mixture. Thus, a simple, efficient, and general procedure has been developed for the synthesis of unsymmetrical diorganyl selenides, sulfides (thioethers), selenoesters, and thioesters by this one-pot reaction at room temperature.
- Ranu, Brindaban C.,Mandal, Tanmay
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p. 5793 - 5795
(2007/10/03)
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- Indium(I) iodide-mediated cleavage of diphenyl diselenide. An efficient one-pot procedure for the synthesis of unsymmetrical diorganyl selenides
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(Matrix presented) A simple and efficient procedure has been developed for the synthesis of unsymmetrical diorganyl selenides through a one-pot indium(I) iodide-mediated reaction of alkyl halide and diphenyl diselenide in methylene chloride at room temperature.
- Ranu, Brindaban C.,Mandal, Tanmay,Samanta, Sampak
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p. 1439 - 1441
(2007/10/03)
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- One-pot synthetic method of unsymmetrical diorganyl selenides: Reaction of diphenyl diselenide with alkyl halides in the presence of lanthanum metal
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A convenient synthetic method of unsymmetrical selenides has been developed. When diphenyl diselenide was allowed to react with two equimolar amounts of primary alkyl iodides and bromides in the presence of an equimolar amount of lanthanum metal, alkyl ph
- Nishino, Toshiki,Okada, Mitsuo,Kuroki, Takamasa,Watanabe, Toshihisa,Nishiyama, Yutaka,Sonoda, Noboru
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p. 8696 - 8698
(2007/10/03)
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- Reductive Cleavage of the Se-Si Bond in Aryiselenotrimethylsilanes: Novel Method for the Synthesis of Unsymmetrical Selenides
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Arylseienotrimethylsilanes are reduced by samarium diiodide to yield samarium areneselenolates, which react with alkyl halidesto give unsymmetrical selenides.
- Zhang, Songlin,Zhang, Yongmin
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p. 350 - 351
(2007/10/03)
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- The Cyclization of Hex-5-enylcarbamates and Related Compounds with Benzeneselenyl chloride and Some Reactions of the 2-Substituted Piperidine Products
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The reaction of hex-5-enylcarbamates with benzeneselenyl chloride gives adducts which cyclize in the presence of silica or stannic chloride, to 2-phenylselenomethylpiperidine derivatives which are unstable, both thermally and on silica.The selenoxides also undergo a Pummerer-type reaction to form 2-acetoxy(phenylseleno)methylpiperidine systems which can be oxidatively converted into a piperidine 2-aldehyde.The selenoxides react with carbon tetrachloride in base to form a 2,2,2-trichloroethyl substituent.Both the selenoxides and the phenylseleno groups of the cyclized products can be displaced by nucleophiles.Ethy hept-6-enylcarbamate did not give a cyclic product with benzeneselenyl chloride and silica, and gave a poor yield of a hexahydroazepine with stannic chloride.Hex-5-enamide cyclized to give a lactone, rather than a lactam, product.Hex-5-enenitrile gave Ritter reaction products with benzeneselenyl chloride in acetonitrile, and a dimer in non-nucleophilic solvents.
- Morella, Angelo M.,Ward, A. David
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p. 445 - 468
(2007/10/02)
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- Thiol/Diselenide Exchange for the Generation of Benzeneselenolate Ion. Catalytic Reductive Ring-Opening of α,β-Epoxy Ketones
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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
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p. 5179 - 5183
(2007/10/02)
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- Oxidation of Alkyl Phenyl Selenides, Tellurides, and Telluroxides with meta-Chloroperbenzoic Acid for a Facile and Novel Transformation of C-Se and C-Te Bonds to C-O Bonds
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In sharp contrast to the well-known selenoxide elimination leading to olefins, the treatment of alkyl phenyl selenides (PhSeR) with an excess of meta-chloroperbenzoic acid (MCPBA; 2-5 equiv. to a selenide) in alcohol at room temperature affords the corresponding dialkyl ethers by the substitution of a phenylselenium (PhSe) moiety with an alkoxy group.A similar reaction proceeds by using alkyl phenyl tellurides (PhTeR) and telluroxides , a facile substitution of PhTe or PhTe(O) moiety by an alkoxy group being observed.Methanol is the most appropriate solvent for these oxidations and alkyl methyl ethers are formed in excellent yields.The reaction is accompanied by phenyl migration when applied to some selenides, tellurides, and telluroxides having a phenyl group at a vicinal position to the PhSe, PhTe, or PhTe(O) moiety.Application to the methoxyselenation and methoxytelluration products of cyclohexene and cycloheptene results in a ring-contraction to afford the dimethyl acetals of cyclopentane- and cyclohexane-carbaldehyde, respectively.In case of an allylic phenyl selenide, a sigmatropic rearrangement giving a rearranged allylic alcohol occurs in much preference to the substitution by the methoxy group.Other oxidizing agents than MCPBA such as NaIO4, H2O2, t-BuOOH, and ozone are generally ineffective under similar conditions.It is proposed that the reaction mainly takes place as follows.Alkyl phenyl selenone, alkyl phenyl tellurone, or the MCPBA addition product to them is formed as a reactive intermediate in which an alkyl C-Se or alkyl C-Te bond fission occurs heterolytically by a nucleophilic attack of alcohol, sometimes accompanied by a 1,2-shift of the β-substituent, i.e., phenyl migration and ring-contraction.
- Uemura, Sakae,Fukuzawa, Shin-ichi
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p. 471 - 480
(2007/10/02)
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- Oxidation of Selenides and Tellurides with Positive Halogenating Species
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Treatment of diaryl or alkyl aryl selenides and diaryl or dialkyl tellurides first with a positive halogen source (N-chlorosuccinimide, tert-butyl hypochlorite) followed by alkaline hydrolysis (10percent sodium hydroxide, saturated sodium bicarbonate) gave the corresponding selenoxides or telluroxides (or hydrates) in good yield.The method is tolerant of a variety of functional groups including esters, olefins, alcohols, ethers, and ketones.The formal oxidation step is believed to be the formation of a chloroselenonium or chlorotelluronium species followed by hydrolysis. 1H NMR evidence is given for a benzylphenylselenonium species. Selenoxide fragmentation reactions during the hydrolysis step were observed
- Detty, Michael R.
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p. 274 - 279
(2007/10/02)
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