Synthesis of diaryl selenides using electrophilic selenium species and nucleophilic boron reagents in ionic liquids

Freitas, Camilo S.; Barcellos, Angelita M.; Ricordi, Vanessa G.; Pena, Jesus M.; Perin, Gelson; Jacob, Raquel G.; Lenardão, Eder J.

doi:10.1039/c1gc15725f

Cited by 62 publications

(28 citation statements)

References 59 publications

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“…In some cases, the relative configurations were confirmed by NOESY experiments. After chromatographic purification the enantiomeric ratios of the resolved alcohols were measured by NMR using Eu(fod) 3 as chiral shift reagent and, in selected examples, they proved to be in perfect agreement with those obtained by HPLC. The yields reported in Table 3 refer to the amount of the product isolated after chromatography as pure compounds (2 or 3) or as mixtures of isomers (4,5).…”

Section: Figurementioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

“…[1][2][3] During the last decades, the synthesis of enantiomerically pure diselenides and their use as precursors of the corresponding electrophilic reagents, has been shown to be a practical and powerful tool for the stereoselective preparation of enantiomerically enriched chiral molecules. [1][2][3][4][5][6][7][8] Some years ago we introduced a new class of enantiopure sulfur-containing diselenides exploring their synthetic applications in enantioselective selenium addition reactions to unsaturated substrates. 9 Electrophilic reagents generated starting from these diselenides were successfully employed in the synthesis of enantiomerically enriched alcohols, 10 ethers, 10 azides, 11 heterocycles 12,13 and, very interestingly, in the kinetic resolution of racemic allylic alcohols through a methoxyselenenylation reaction.…”

Section: Introductionmentioning

confidence: 99%

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Kinetic resolution of 2-methoxycarbonylalk-3-enols through a stereoselective cyclofunctionalization promoted by an enantiomerically pure electrophilic selenium reagent

Tomassini¹,

Sarra²,

Monti³

et al. 2016

Arkivoc

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In this manuscript the kinetic resolution of 2-methoxycarbonylalk-3-enols is reported through a stereoselective selenocyclization promoted by an electrophilic sulfur-containing selenium reagent. Reacting one equivalent of the selenenenylating agent with two equivalents of racemic starting material afforded a mixture of a stereoselectively enriched tetrahydrofuran and the corresponding enantiomerically enriched alkenols.

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Section: Figurementioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Kinetic resolution of 2-methoxycarbonylalk-3-enols through a stereoselective cyclofunctionalization promoted by an enantiomerically pure electrophilic selenium reagent

Tomassini¹,

Sarra²,

Monti³

et al. 2016

Arkivoc

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“…Different groups prepared diorganyl selenides and selenolesters in a series of dialkylimidazolium ILs employing different promoters and catalysts as Zn dust, ZnO nanopowder, CuO nanopowder, NaBF 4 , Indium and InI, triphenyl phosphine, palladium, or the bimetallic reagent Sn(II)/Cu(II) . The use of [bmim][BF 4 ] and [bmim][PF 6 ] in the synthesis of diaryl selenides by electrophilic substitution in arylboron reagents with phenylselenyl halides has been also described . In addition, a series of chiral seleno amino derivatives have been synthesized employing CuO nanopowder in the IL [bmim][BF 4 ] .…”

Section: Introductionmentioning

confidence: 99%

A mild and efficient procedure for alkenols oxyselenocyclization by using ionic liquids

Kostić

Verdía

Fernández-Stefanuto

et al. 2019

J of Physical Organic Chem

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A mild and efficient procedure for the oxyselenocyclization of unsaturated alcohols by treatment with phenylselenyl chloride using ionic liquids as solvents/catalyzers has been developed. The reaction proceeds instantaneously under mild conditions with absolute regioselectivity, using primary, secondary, tertiary, and aromatic alcohols, as well as monosubstituted, disubstituted, and trisubstituted alkenols. This procedure provides a new method for the synthesis of substituted tetrahydrofurans and tetrahydropyrans ethers, the precursors of many biologically active metabolites, avoiding the use of toxic and corrosive catalysts. There are no previous reports of seleniummediated cyclofuncionalization reactions in ionic liquids. Taking into the account the good results obtained with [MMIM][MSO 4 ], its ease preparation, low viscosity, low price, and its capacity to be recovered and reused, it was selected as the solvent/catalyzer. Quantum-chemical calculations (MP2(fc)/ 6-311 + G**//B3LYP/6-311 + G**) has shown that the intramolecular cyclization is promoted by the hydrogen bond formed between the ionic liquid anion and the hydroxyl group of the alkenol.

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“…Bhadra et al [54] introduced alumina-supported copper-mediated nucleophilic displacement of phenylselenium bromide as an alternative precursor for the synthesis of different kinds of aryl selenides. Lenardo and coworkers [55] disclosed the use of imidazolium ionic liquids for the synthesis of diaryl selenides from electrophilic selenium species and nucleophilic boron reagents under a N 2 atmosphere. Recently, transition-metal-free unsymmetrical diaryl chalcogenides from arenes and dichalcogenides has been reported by using persulfate oxidant and trifluoroacetic acid solvent.…”

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confidence: 99%

Copper Nanoparticles Catalyzed Se(Te)Se(Te) Bond Activation: A Straightforward Route Towards Unsymmetrical Organochalcogenides from Boronic Acids

et al. 2014

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A highly porous copper metal-organic framework, [Cu 3 (BTC) 2 ] (BTC = benzene-1,3,5-tricarboxylate) was synthesized and used as a precursor for the synthesis of copper nanoparticles (NPs) and characterized by several techniques, including XRD, SEM, TEM, EDX and BET measurements. The as-synthesized copper nanoparticles were immobilized onto activated charcoal (AC) by means of ultrasonication at room temperature without any pretreatment. The Cu NPs/AC was employed as a heterogeneous catalyst for the cross-coupling of diphenyl diselenide and boronic acids to form diphenyl selenides through SeÀSe bond activation under ligand-, base-, and additive-free conditions. The copper NPs/AC, which combines the architecture of MOFs and the high surface area of charcoal, could be an efficient heterogeneous catalytic system that is compatible with a variety of substituents on diphenyl selenides. Its promising catalytic activity relative to that of other homogeneous systems and low catalyst loading for the synthesis of unsymmetrical diaryl selenides is an important application in the area of nanocatalysis. The Cu NPs/AC catalyst, which exhibits excellent catalytic activity and remarkable tolerance to a wide variety of substituents, led to Se sp 3 -, sp 2 -, and sp-carbon bond formation by using DMSO as a solvent and atmospheric air as oxidant. This approach can also be extended to the preparation of unsymmetrical organotelluride derivatives.Copper catalysts for cross-coupling reactions are an intense field of research because they are cost-effective and hold promise for the replacement of expensive metal sources for industrial purposes. Over the past decade, the construction of carbonÀselenium bonds has been an intriguing topic for researchers and the number of related publications has increased exponentially to date, mainly owing to the important therapeutic characteristics of these bonds, such as their antimicrobial, antiviral, antitumor, and antioxidant properties. In addition, chalcogens are important constituents of functional groups in biomolecules (i.e., those associated with redox chemistry) in eukaryotic biochemistry.[1] Moreover, seleniumbased ionic liquids have proven to be efficient catalysts in reactions such as the carbonylation of aniline, oxidation of thiols, syntheses of octahydroacridines and thioacetals, and the Baylis-Hillman reaction of aldehydes and electron-deficient alkenes. [2][3][4][5][6][7] Over the past decade, extensive work has been devoted to developing new methodologies for the creation of bonds between sp 3 -, sp 2 -, sp-carbon atoms and organochalcogens, especially selenium-and tellurium-based compounds. To synthesize these moieties, a number of synthetic methods have been reported so far. [8][9][10][11][12][13][14][15][16][17][18][19][20][21][22] Of these, two methods are generally used. These methods involve the use of diphenyl diselenide (telluride) as starting precursor owing to its stability in air, environmental friendliness, and commercial availability. Diphenyl diselenide can be reacted w...

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Synthesis of diaryl selenides using electrophilic selenium species and nucleophilic boron reagents in ionic liquids

Cited by 62 publications

References 59 publications

Kinetic resolution of 2-methoxycarbonylalk-3-enols through a stereoselective cyclofunctionalization promoted by an enantiomerically pure electrophilic selenium reagent

Kinetic resolution of 2-methoxycarbonylalk-3-enols through a stereoselective cyclofunctionalization promoted by an enantiomerically pure electrophilic selenium reagent

A mild and efficient procedure for alkenols oxyselenocyclization by using ionic liquids

Copper Nanoparticles Catalyzed Se(Te)Se(Te) Bond Activation: A Straightforward Route Towards Unsymmetrical Organochalcogenides from Boronic Acids

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