- Method for synthesizing asymmetric selenide through selenol catalytic reaction
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The invention discloses a method for synthesizing asymmetric selenide through selenol catalytic reaction. The method comprises the following steps: (1) sequentially adding anhydrous N, N-dimethylformamide, zinc chloride, phenylselenol, a strong base, halogenated hydrocarbon and a 4A molecular sieve into a reaction container; (2) stirring and reacting for 20-40 hours at normal temperature in an oxygen-free state; (3) filtering, and removing N, N-dimethylformamide and halogenated hydrocarbon to obtain a stock solution; and (4) diluting the stock solution obtained in the step (3) with diethyl ether, washing with water, drying, and distilling off the diethyl ether to obtain the asymmetric selenide. According to the method for synthesizing the asymmetric selenide provided by the invention, the low-proportion zinc chloride is adopted for reaction, so that the final product asymmetric selenide can be efficiently obtained with high yield; the method has the advantages that the use of cesium base, namely cesium hydroxide, which is not easy to commercialize or is very uneconomical is avoided, harsh reaction conditions are also avoided, the mild reaction conditions are adopted, the reaction time is greatly shortened, the atom economy is realized, and the yield of the finally obtained asymmetric selenide is relatively high.
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Paragraph 0035-0042
(2021/07/09)
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- Production of Alkyl Aryl Sulfides from Aromatic Disulfides and Alkyl Carboxylates via a Disilathiane–Disulfide Interchange Reaction
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The results of this study show that disilathiane is an effective mediator in the synthesis of alkyl aryl sulfides with disulfides and alkyl carboxylates. Mechanistic studies suggest that disilathiane promotes cleavage of the sulfur–sulfur bond of disulfides to generate thiosilane as a key intermediate. Diselenides were also applicable to this transformation to produce the corresponding selenides.
- Nakajima, Takumi,Takano, Ken,Maeda, Hiromu,Ogiwara, Yohei,Sakai, Norio
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supporting information
p. 4103 - 4107
(2021/11/10)
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- O-(tert-butyl) Se-phenyl selenocarbonate: A convenient, bench-stable and metal-free precursor of benzeneselenol
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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
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- Copper-Catalyzed Three-Component Coupling Reaction of Aryl Iodides, a Disilathiane, and Alkyl Benzoates Leading to a One-Pot Synthesis of Alkyl Aryl Sulfides
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A copper-catalyzed three-component coupling reaction of aryl iodides, hexamethyldisilathiane and alkyl benzoates leading to alkyl aryl sulfides has been demonstrated. A disilathiane acted as both a sulfur source and a promoter of the sulfidation, and the alkyl moiety of the alkyl benzoate was effectively introduced on one side of the sulfide. Moreover, we found that the protocol can be expanded to the preparation of ethyl phenyl selenide with diphenyl diselenide.
- Sakai, Norio,Maeda, Hiromu,Ogiwara, Yohei
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p. 2323 - 2330
(2019/05/24)
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- Corey-Chaykovsky Cyclopropanation of Nitronaphthalenes: Access to Benzonorcaradienes and Related Systems
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Nitronaphthalene derivatives react as Michael acceptors in the Corey-Chaykovsky reaction with alkyl phenyl selenones and alkyl diphenyl sulfonium salts. Mechanistic studies reveal that sterically demanding substituents at the carbanionic center favor formation of cyclopropanes and suppress competitive β-elimination to the alkylated products. The transformation, demonstrated also on heterocyclic nitroquinoline and nitroindazolines, is an example of transition metal-free dearomatization method.
- Antoniak, Damian,Barbasiewicz, Micha?
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supporting information
p. 9320 - 9325
(2019/11/19)
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- α-Alkylation of tertiary amines by C(sp3)–C(sp3) cross-coupling under redox neutral photocatalysis
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Direct α-alkylation of N-phenyl-tetrahydroisoquinoline with alkyl selenides of desired alkyl chain length and functionality is reported by photoredox catalysis. Construction of hexahydro pyrrolo- and pyrido-isoquinoline scaffolds along with indolines and tetrahydroquinolines is also described by intramolecular C(sp3)–C(sp3) cross-couplings.
- Pandey, Ganesh,Tiwari, Sandip Kumar,Singh, Bhawana
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supporting information
p. 4480 - 4483
(2016/09/14)
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- Radical intermediates in the Zn-promoted Barbier-type alkylation of diphenyl diselenide in aqueous medium
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The zinc promoted Barbier-type reaction of alkyl halides and diphenyl diselenide in aqueous medium leads to high yields of mixed selenides even in acidic medium. Especially the efficient formation of t-butylphenylselenide cannot be explained by nucleophil
- Dos Anjos, Jose Ayron Lira,Bieber, Lothar Wilhelm
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p. 6492 - 6494,3
(2012/12/12)
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- Zn in ionic liquid: An efficient reaction media for the synthesis of diorganyl chalcogenides and chalcogenoesters
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A straightforward and efficient methodology is described to synthesize structurally diverse diorganyl selenides, sulfides, seleno- and thioesters by using commercially available Zn dust in ionic liquid. Excellent yields were achieved under neutral conditions at room temperature in a short time. The solvent/ionic liquid is reusable and exhibited higher performance as compared with organic solvents.
- Narayanaperumal, Senthil,Alberto, Eduardo E.,Gul, Kashif,Kawasoko, Cristiane Yuriko,Dornelles, Luciano,Rodrigues, Oscar E.D.,Braga, Antonio Luiz
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experimental part
p. 4723 - 4730
(2011/06/27)
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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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- Synthesis of diorganyl selenides mediated by zinc in ionic liquid
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Figure presented A new approach for the synthesis of diorganyl selenides is described. By using economically attractive zinc dust in BMIM-BF4, a series of diorganyl selenides were efficiently achieved in excellent yields, under neutral reaction conditions. Compared to the usual organic solvents, BMIM-BF4 exhibited higher performance with the advantage to be reused up to five successive runs.
- Narayanaperumal, Senthil,Alberto, Eduardo E.,Gul, Kashif,Rodrigues, Oscar E. D.,Braga, Antonio L.
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supporting information; experimental part
p. 3886 - 3889
(2010/07/05)
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- Ionic liquid: An efficient and recyclable medium for synthesis of unsymmetrical diorganyl selenides promoted by InI
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In an environmentally friendly protocol, InI was used as a reducing agent for the Se-Se bond to prepare unsymmetrical diorganyl selenides with very short reaction times, mild conditions and excellent yields using (bmim)BF4 as a recyclable solvent.
- Narayanaperumal, Senthil,Alberto, Eduardo E.,De Andrade, Fabiano Molinos,Lenardao, Eder J.,Taube, Paulo S.,Braga, Antonio L.
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experimental part
p. 4647 - 4650
(2009/12/08)
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- 1-(organoselanyl)perfluoroalkanols: A stable and efficient precursor for organoselenols
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The 1-(organoselanyl)perfluoroalkanols 1, 3, 4, and 10 were successfully prepared and reactions with hexanoyl chlorides to produce the corresponding esters 5, 7, and 8, accompanied by the selenoesters 6 were conducted. The DBU-mediated alkylations of the heptafluorobutanols 4, 10, and the α-p-nitro-benzoate 2 with alkyl halides easily provided alkyl phenyl selenides 9a-9i and 11a-11c in good to high yields. Copyright
- Yamamoto, Terahisa,Moriura, Eri,Sawa, Arisa,Yoshimatsu, Mitsuhiro
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scheme or table
p. 1046 - 1047
(2009/12/03)
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- Preparation of the first bench-stable phenyl selenolate: An interesting "on water" nucleophilic reagent
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In this communication we report the synthesis and the characterization of the first solid and air-stable selenolates, starting from commercially available phenylselenenyl halides and elemental zinc. These reagents were efficiently employed in the ring ope
- Santi, Claudio,Santoro, Stefano,Battistelli, Benedetta,Testaferri, Lorenzo,Tiecco, Marcello
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scheme or table
p. 5387 - 5390
(2009/05/07)
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- A simple zinc-mediated preparation of selenols
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Under acidic conditions zinc reduces diselenides to afford selenols, which can be either isolated or treated in situ with alkyl halides to produce alkyl selenides or with epoxides to give β-hydroxyselenides. Georg Thieme Verlag Stuttgart.
- Santi, Claudio,Santoro, Stefano,Testaferri, Lorenzo,Marcello Tiecco
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scheme or table
p. 1471 - 1474
(2009/04/07)
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- Aqueous phase one-electron reduction of sulfonium, selenonium and telluronium salts
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Triorganylsulfonium, -selenonium and -telluronium salts were reduced by carbon dioxide radical anions/solvated electrons produced in aqueous solution by radiolysis. The radical expulsion accompanying reduction occurred with the expected leaving group propensities (benzyl > secondary alkyl > primary alkyl > methyl > phenyl), although greater than expected loss of the phenyl group was often observed. Diorganyl chalcogenides formed in the reductions were conveniently isolated by extraction with an organic solvent. Product yields based on the amount of reducing radicals obtained from the γ-source were often higher than stoichiometric (up to 1800 %) in the reduction of selenonium and telluronium compounds; it is likely that this result can be accounted for in terms of a chain reaction with carbon-centred radicals/formate serving as the chain transfer agent. The product distribution was essentially independent of the reducing species for diphenyl alkyl telluronium salts, whereas significant variations were seen for some of the corresponding selenonium salts. This would suggest the intermediacy of telluranyl radicals in the one-electron reduction of telluronium salts. However, pulse radiolysis experiments indicated that the lifetimes of such a species (the triphenyltelluranyl radical) would have to be less than 1 μs. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005.
- Eriksson, Per,Engman, Lars,Lind, Johan,Merenyi, Gabor
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p. 701 - 705
(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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- General synthesis of alkyl phenyl selenides from organic halides mediated by zinc in aqueous medium
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Organic halides of different structural types react with diphenyl diselenide and zinc dust in aqueous medium to give alkyl phenyl selenides. Benzylic and allylic bromides, α-bromoesters, acids and ketones and some primary alkyl iodides produce high yields even under acidic conditions. Less reactive halides need basic medium. The reaction proceeds equally well in the presence of various unprotected functional groups. Control experiments support a SH2 mechanism via alkyl radicals.
- Bieber, Lothar W.,De Sá, Ana C.P.F.,Menezes, Paulo H.,Gon?alves, Simone M.C.
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p. 4597 - 4599
(2007/10/03)
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- Thermal reactions of organyl chalcogenides with α,β-unsaturated aldehydes
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Thermalgas-phase reactions of acrolein, cinnamaldehyde, and benzaldehyde with diorganyl chalcogenides and diorganyl dichalcogenides were studied.Acrolein does not react with chalcogenides at 300-600 deg C but completely decomposes under reaction conditions.At 600-650 deg C, cinnamaldehyde reacts only with diorganyl selenides and diselenides to give benzoselenophene.Its highest yield (53percent) is achieved in the reaction with dimethyl diselenide at 630 deg C and at an equimolar ratio of the reactants.The gas-phase reactions of benzaldehyde at 400-500 deg C afford chalcogen-containing derivatives of several types, among which thioanisole and its selenium or tellurium analogs predominate.The mechanisms of the above reactions were discussed in terms of homolytic substitution of the formyl group at unsaturated carbon atoms by chalcogenyl radicals. - Keywords: gas-phase reactions; cinnamaldehyde; benzaldehyde; chalcogenyl radicals; benzoselenophene, selenoanisole, telluroanisole.
- Deryagina, E. N.,Korchevin, N. A.,Shilkina, T. A.,Sukhomazova, E. N.,Levanova, E. P.
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p. 447 - 450
(2007/10/03)
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- Reaction of 5-hexenyltributyltin with pseudohalogens: cyclization vs. double bond addition
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Reaction of 5-hexenyltributyltin with pseudohalogen electrophiles leads to either double bond addition products or cyclization products.When electrophiles containing non-nucleophilic counterions are used, predominately cyclization products are formed.
- Herndon, James W.,Harp, Jill J.
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- SYNTHESIS OF α-SELENOALKYLLITHIUM COMPOUNDS
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α-Phenylselenoalkyllithiums and α-methylselenoalkyllithiums have been prepared from the corresponding selenoacetals and alkyllithiums.Several features of this reaction are disclosed.For example, the reaction is more readily achieved on phenylselenoacetals than on methylseleno analogues.Those derived from hindered carbonyl compounds are less readily cleaved. s-BuLi/THF proved superior to n-BuLi in THF, itself better than n-BuLi in ether.
- Krief, A.,Dumont, W.,Clarembeau, M.,Bernard, G.,Badaoui, E.
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p. 2005 - 2022
(2007/10/02)
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- NUCLEOPHILIC VINYLIC SUBSTITUTIONS ON UNACTIVATED SUBSTRATES. THE BEHAVIOUR OF STYRYL ALKYL SULPHIDES AND SELENIDES TOWARDS SULPHUR AND SELENIUM NUCLEOPHILES
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Sodium alkanethiolates or lithium methyl selenide react with styryl alkyl sulphides and selenides, in DMF at 100 deg C, to give the products of vinylic or aliphatic substitution.The two nucleophilic reagents are extremely selective.In the case of RSNa the
- Testaferri, L.,Tiecco, M.,Tingoli, M.,Chianelli, D.
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p. 1401 - 1408
(2007/10/02)
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- Phenyl Selenide Anion, a Superior Reagent for the SN2 Cleavage of Esters and Lactones
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The scope and limitations of SN2-type cleavages of esters and lactones with phenyl selenide anion are discussed.The reagent, when generated properly, is found to be an extremely potent nucleophile.However, its nucleophilicity can be greatly attenuated by varying the counterion and/or the degree of solvation of the anion.The reagent can be used in the presence of a variety of functional groups and exhibits a high degree of selectivity; e.g., methyl esters are selectively cleaved in the presence of ethyl esters.As the hindrance around the carbinol carbon increases, products derived from acyl oxygen cleavage are observed.The mechanistic implications of this are discussed.
- Liotta, Dennis,Sunay, Ustun,Santiesteban, Hector,Markiewicz, William
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p. 2605 - 2610
(2007/10/02)
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