- Straightforward and direct access to β-seleno- amines and sulfonylamides via the controlled addition of phenylselenomethyllithium (LiCH2SePh) to imines
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The transfer of a α-methyl phenylseleno carbanion to variously functionalized N-aryl and N-sulfonyl imines is reported. The fast selenium-lithium exchange conducted on a diselenoacetal with n-BuLi enables the generation of the attacking homologative nucleophile under chemoselective conditions preserving concomitant potentially sensitive functionalities to the lithiating conditions. Uniformly high yields were observed, thus establishing a valuable and conceptually simple approach to the title compounds.
- Senatore, Raffaele,Malik, Monika,Touqeer, Saad,Listro, Roberta,Collina, Simona,Holzer, Wolfgang,Pace, Vittorio
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Read Online
- Photoinduced syntheses and reactivities of phosphorus-containing interelement compounds
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The photoinduced reactions of tetraphenyldiphosphine disulfide with a range of organic dichalcogenides successfully afforded a series of phosphorus(V)-chalcogen interelement compounds via a radical process. The relative reactivities of the organic dichalcogenides (i.e., (PhS)2, (PhSe)2, and (PhTe)2) toward the PIII or PV groups in the diphosphine analogues under light were investigated in detail, and a convenient method was developed to form P-S or P-Se interelement compounds from tetraphenyldiphosphine disulfide and (PhS)2 or (PhSe)2 upon photoirradiation. Furthermore, the relative photochemical properties and reactivities of tetraphenyldiphophine (P- P interelement compound) and its analogues toward photoinduced radical addition reactions were also discussed. The formed P-E (E = S, Se) interelement compounds could be utilized for ionic reactions, and they could be transformed into various phosphine reagents via one-pot processes.
- Yamamoto, Yuki,Tanaka, Ryo,Ota, Miyuto,Nishimura, Misaki,Tran, Cong Chi,Kawaguchi, Shin-Ichi,Kodama, Shintaro,Nomoto, Akihiro,Ogawa, Akiya
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p. 14708 - 14719
(2020/11/13)
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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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- Reactivity of a β-diketiminate-supported magnesium alkyl complex toward small molecules
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The reactivity of the magnesium alkyl {[HC(C(Me)N-2,6-iPr2C6H3)2]Mg(nBu)}2 (1) toward various small molecules provides access to a variety of magnesium derivatives. For example, the insertion of elemental chalcogens (S8 and Se8) into the Mg-C bond of complex 1 gives the dimeric magnesium thiolate {[HC(C(Me)N-2,6-iPr2C6H3)2]Mg(μ-SnBu)}2 (2), magnesium selenolate [HC(C(Me)N-2,6-iPr2C6H3)2]Mg(SenBu)(THF) (3), and magnesium diselenolate [HC(C(Me)N-2,6-iPr2C6H3)2]Mg(Se2nBu)(THF) (4). Meanwhile, compound 4 can be readily obtained by further insertion of one selenium atom into complex 3. Moreover, the reactions of complex 1 with diphenyl dichalcogenides (PhSSPh and PhSeSePh) by σ bond metathesis afford the corresponding magnesium phenyl chalcogenolates [HC(C(Me)N-2,6-iPr2C6H3)2]Mg(EPh)(THF) (E = S 5, Se 6) concomitant with PhEnBu release. Furthermore, the treatment of complex 1 with benzonitrile and phenyl isothiocyanate produces the serendipitous magnesium-1-azaallyl complex [HC(C(Me)N-2,6-iPr2C6H3)2]Mg(N(H)C(Ph)CHC3H7)(DME) (7) and the diimino-thioamidato magnesium compound {κ3-N,N′,N′′-(ArNCMe)2[N(Ph)CS]CH}Mg[(Ph)NC(nBu)S] (8) (Ar = 2,6-iPr2C6H3). In addition, deprotonation occurs between compound 1 and 1-methylimidazole to generate the imidazolyl complex {[HC(C(Me)N-2,6-iPr2C6H3)2]Mg(μ-Im)}2 (9) (Im = 2-N-methylimidazolyl). These results indicated that the butylmagnesium complex 1 possesses high activity toward small molecules and revealed several unusual transformations. All the new compounds were characterized by various spectroscopic methods, and their solid-state structures were further confirmed by single-crystal X-ray diffraction analyses.
- Ren, Wenshan,Zhang, Shaohui,Xu, Ziyi,Ma, Xuebing
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supporting information
p. 3109 - 3115
(2019/03/06)
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- 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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- Mechanistic Insight into the Oxidation of Organic Phenylselenides by H2O2
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The oxidation of organic phenylselenides by H2O2is investigated in model compounds, namely, n-butyl phenyl selenide (PhSe(nBu)), bis(phenylselanyl)methane (PhSeMeSePh), diphenyl diselenide (PhSeSePh), and 1,2-bis(phenylselanyl)ethane
- Ribaudo, Giovanni,Bellanda, Massimo,Menegazzo, Ileana,Wolters, Lando P.,Bortoli, Marco,Ferrer-Sueta, Gerardo,Zagotto, Giuseppe,Orian, Laura
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p. 2405 - 2422
(2017/02/23)
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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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- A general and green procedure for the synthesis of organochalcogenides by CuFe2O4 nanoparticle catalysed coupling of organoboronic acids and dichalcogenides in PEG-400
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A general and efficient procedure has been developed for the synthesis of organochalcogenides (selenides and tellurides) by a simple reaction of organoboronic acids and dichalcogenides catalysed by CuFe2O 4 nanoparticles in PEG-400 without any ligand. This protocol offers the scope for access to a wide spectrum of chalcogenides including diaryl, aryl-heteroaryl, aryl-styrenyl, aryl-alkenyl, aryl-allyl, aryl-alkyl and aryl-alkynyl versions. The catalyst is magnetically separable and recyclable eight times without any loss of appreciable catalytic activity. The products are obtained in high purities after evaporation of solvent followed by filtration column chromatography. The Royal Society of Chemistry.
- Kundu, Debasish,Mukherjee, Nirmalya,Ranu, Brindaban C.
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p. 117 - 125
(2013/04/10)
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- An efficient one-pot approach to selenides: CuI-catalyzed reactions of magnesium selenolate with aryl or alkyl halides
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An efficient one-pot route to symmetrical selenides in GC with yields from 13 to 94% has been developed by CuI catalyzing reactions of magnesium organoselenolates with aryl or alkyl halides under mild conditions. It is suggested that selenium could leave from PhSeMgBr to form other RSeMgBr with RMgBr based on experimental results. Although the leaving selenium causes low yield of unsymmetrical selenides and complex products, it offers a slowly releasing selenium source in preparation of nano metal selenides, and a potential leaving group in nucleophilic substitution. The role of excess magnesium is proposed.
- Gao, Fei,Tang, Yu,Lin, Hemei,Yang, Jun,Zhang, Yuanming
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p. 787 - 793
(2013/07/26)
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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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- Palladium-catalyzed cross-coupling of PhSeSnBu3 with aryl and alkyl halides in ionic liquids: A practical synthetic method of diorganyl selenides
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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
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experimental part
p. 2661 - 2665
(2012/01/04)
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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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- Efficient ring opening of protected and unprotected aziridines promoted by stable zinc selenolate in ionic liquid
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A highly efficient protocol is reported for the synthesis of chiral β-seleno amines via the ring-opening reaction of aziridines. Under neutral conditions, employing a stable phenyl selenolate specie (PhSeZnBr) and (BMIM)BF4 as solvent, β-seleno
- Salman, Syed M.,Schwab, Ricardo S.,Alberto, Eduardo E.,Vargas, Josimar,Dornelles, Luciano,Rodrigues, Oscar E. D.,Braga, Antonio L.
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supporting information; scheme or table
p. 69 - 72
(2011/02/25)
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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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- Al2O3-Supported Cu-catalyzed electrophilic substitution by PhSeBr in organoboranes, organosilanes, and organostannanes. A protocol for the synthesis of unsymmetrical diaryl and alkyl aryl selenides
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(Figure Presented) Alumina-supported copper sulfate efficiently catalyzes electrophilic substitution in organoborane, organosilanes, and organostannanes by phenylselenium bromide providing a novel and efficient route to the synthesis of unsymmetrical diaryl and alkyl aryl selenides. A series of aryl, alkyl, and heteroaryl phenyl selenides were obtained in high yields. The catalyst is inexpensive, eco- and user-friendly, and recyclable. The mechanism involving Cu-assisted nucleophilic displacement of Br in PhSeBr by mild nucleophiles is described.
- Bhadra, Sukalyan,Saha, Amit,Ranu, Brindaban C.
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experimental part
p. 4864 - 4867
(2010/10/18)
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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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- On the reactivity of indium(III) benzenechalcogenolates (chalcogen = sulfur and selenium) towards organyl halides for the synthesis of organyl phenyl chalcogenides
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The reactivity of indium(III) benzenechalcogenolates (chalcogen = sulfur, selenium) towards organyl halides (organyl = alkyl, allyl, benzyl, acyl) was examined. A practical one-pot method to prepare organyl phenyl chalcogenides indium metal and diphenyl dichalcogenide was found. The coupling is fairly broad in scope and generally works better organyl halides capable to produce stable carbocations.
- Peppe, Clovis,Borges De Castro, Lierson
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experimental part
p. 678 - 683
(2009/10/30)
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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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- 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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- Deoxygenation of sulfoxides, selenoxides, telluroxides, sulfones, selenones and tellurones with Mg-MeOH
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The deoxygenation of a variety of sulfoxides, selenoxides, telluroxides, sulfones, selenones and tellurones has been reported with Mg-MeOH at room temperature in nearly quantitative yields. The deoxygenation is proposed to proceed by SET from Mg to the substrate.
- Khurana, Jitender M.,Sharma, Vandana,Chacko, Silvi A.
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p. 966 - 969
(2007/10/03)
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- Convenient synthesis of unsymmetrical organochalcogenides using organoboronic acids with dichalcogenides via cleavage of the S-S, Se-Se, or Te-Te bond by a copper catalyst
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(Chemical Equation Presented) This article describes the methodology for a copper-catalyzed preparation of numerous monochalcogenides from dichalcogenides with organoboronic acids. Unsymmetrical diorgano-monosulfides, selenides, and tellurides can be synthesized by the coupling of dichalcogenides with aryl- or alkylboronic acids using a copper catalyst in air. The present reaction can take advantage of both organochalcogenide groups on dichalcogenide.
- Taniguchi, Nobukazu
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p. 1241 - 1245
(2007/10/03)
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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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- Reductive cleavage of Se-Se bond by Sm/NiCl2 or Sm/NiCl 2.6H2O system: A novel preparation of unsymmetrical aryl selenides
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The Sm/NiCl2 or Sm/NiCl2.6H2O system promoted diarylselenides to react with alkyl halides to afford unsymmetrical aryl selenides in good yields under mild and neutral conditions.
- Chen,Su
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p. 958 - 959
(2007/10/03)
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- A novel synthesis of unsymmetrical selenides via the cleavage of Se-Se bond by Sm/cat.CoCl2 system
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Promoted by Sm/cat. CoCl2 system, the Se-Se bond of diaryldiselenides was easily cleaved to form a "living" intermediate, which reacted readily with alkyl halides to afford unsymmetrical alkylarylselenides in good yields under mild and neutral reaction conditions.
- Chen, Rener,Su, Weike,Zhong, Weihui
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p. 620 - 621
(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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- Synthesis of chalcogenides using indium intermediates in aqueous media
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Selenides and vinylic selenides were synthesized from their corresponding organic halides and alkynes in aqueous media using indium metal.
- Galindo, Andréa C.,Oliveira, Juliana M.,Barboza, Maria A. G.,Gon?alves, Simone M. C.,Menezes, Paulo H.
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p. 129 - 140
(2007/10/03)
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- Toward the synthesis of the antibiotic tetrodecamycin
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We report here a short approach to a tricyclic substructure of tetrodecamycin exhibiting a unique ring skeleton utilising an acid catalysed ring closure as the key step. In addition an efficient three-step synthesis of 5-alkylidene 4-methoxy-2(5H)-furanones starting from 4-methoxy-2(5H)-furanone is described. (C) 2000 Elsevier Science Ltd.
- Paintner,Bauschke,Kestel
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p. 9977 - 9980
(2007/10/03)
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- New synthetic method of diorganyl selenides: Palladium-catalyzed reaction of PhSeSnBu3 with aryl and alkyl halides
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(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
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p. 1725 - 1727
(2008/02/11)
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- Reductive Cleavage of the Se-Se Bond by the Sm-Me3SiCl-H2O System: Preparation of Unsymmetrical Phenyl Selenides
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The reduction of diphenyl diselenide by the Sm-Me3SiCl-H2O system led to a selenide anion. This 'living' species reacted with organic halides, epoxides, α,β-unsaturated esters and α,β-unsaturated nitrtles to afford unsymmetrical phenylselenides in good yields under mild and neutral conditions.
- Wang, Lei,Zhang, Yongmin
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p. 598 - 599
(2007/10/03)
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- A New Approach to the Synthesis of Symmetrical Bis(organylchalcogeno)acetylenes: Scope and Limitations
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A new general method to prepare bis(organylchalcogeno)acetylenes R-Y-CC-Y-R (Y = S, Se, Te) by dehydrochlorination of the corresponding 1,2-bis(organylchalcogeno)chloroethylenes R-Y-CH=CCl-Y-R with tert-BuOK/tert-BuOH and/or KOH/DMSO is developed.Dechlorination of 1,2-bis(organylchalcogeno)-1,2-dichloroethylenes R-Y-CCl=CCl-Y-R (Y = S, Se, Te) with BuLi in ether or THF is effective only for sulfur derivatives.With Y = Se and alkyl substituents, substitution of the chlorine atom by a butyl group takes place giving rise to 5,6-bis(alkylseleno)dec-5-ene .With aryl substituents, an attack of the ArSe-group by the Bu-radical is observed leading to an aryl butyl selenide.In the case of the tellurium compound Ph-Te-CCl=CCl-Te-Ph, there is a competition between dechlorination to give Ph-Te-CC-Te-Ph, and substitution to produce the phenyl butyl telluride. - Keywords: bis(organylchalcogeno)acetylene; 1,2-bis(organylchalcogeno)chloroethylene; 1,2-bis(organochalcogeno)-1,2-dichloroethylene.
- Martynov, Alexander V.,Guillanton, Georges Le
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p. 823 - 831
(2007/10/03)
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- Preparation and interconversion of phenylselenenylated and alkyjlselenenylated aromatic compounds
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Phenylselenenyl and alkylselenenyl sulfates were found to efficiently and mildly introduce one or several phenylselenenyl or alkylselenenyl groups into activated aromatic or heteroaromatic compounds. When treated with methylselenenyl sulfate, veratrole an
- Engman, Lars,Eriksson, Per
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p. 861 - 871
(2007/10/03)
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- A convenient procedure for the preparation of organic selenides
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Treatment of diphenyl diselenide with tributylphosphine in an alkaline medium forms phenylselenolate ion which converts alkyl halides, α,β-unsaturated ketones, and epoxides into alkyl selenides, (phenylseleno)alkenones, and β-(phenylseleno)alkanols, respe
- Sakakibara,Katsumata,Watanabe,Toru,Ueno
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p. 377 - 379
(2007/10/02)
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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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- Reactions of Alkylmercurials with Heteroatom-Centered Acceptor Radicals
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The relative reactivities of alkylmercury halides toward PhS., PhSe., or I. decrease drastically from R = tert-butyl to R = sec-alkyl to R = n-butyl, indicative that R. is formed in the rate-determining step in the attack of these radicals upon RHgCl.The alkyl radicals thus formed will enter into chain reactions in which a heteroatom-centered radical (A.) is regenerated from substrates such as RS-SR, ArSe-SeAr, ArTe-TeAr, PhSe-SO2Ar, Cl-SO2Ph; ZCH=CHA (A = Cl, I, SPh, SO2Ph); or PhCCHA (A = I, SPh, SO2Ph). β-Styrenyl (PhCH=CHA, Ph2C=CHA) and β-phenethynyl (PhCCA) systems with A = I, Br, SO2Ph also enter into chain reactions with mercury(II) salts with the ligands PhS, PhSe, PhSO2, or (EtO)2PO.The relative reactivities of a series of reagents toward t-Bu. and of PhCH=CHA, Ph2C=CHA, and PhCCA toward c-C6H11. are reported as well as the regioselectivity of t-Bu. attack observed for 1,2-disubstituted ethylenes (ZCH=CHA) with Z and A from the group Ph, Cl, Br, I, SO2Ph, SPh, Bu3Sn.Reactions of (E)- and (Z)-PhCH=CHI or MeO2CCH=CHI with t-Bu. or c-C6H11. occurred in a regioselective and stereospecific (retention) manner.Reactions of (E)- and (Z)-ClCH=CHCl occurred in a nonstereospecific manner in which the E/Z product ratio increased with the bulk of the attacking radical.A similar effect on the E/Z product ratios was observed for (Z)-MeO2CCH=CHCl.
- Russell, Glen A.,Ngoviwatchai, Preecha,Tashtoush, Hasan I.,Pla-Dalmau, Anna,Khanna, Rajive K.
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p. 3530 - 3538
(2007/10/02)
-
- Aryl Arylazo Sulfones Chemistry. 2. Reactivity toward Alkaline Alkane- and Areneselenolate and Alkane- and Arenetellurolate Anions
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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.
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p. 5196 - 5198
(2007/10/02)
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- The Synthesis and Some Reactions of Thiazolidine-2-selones
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As a route to thiazolidine-2-selones or the tautomeric 2-thiazolines, the reactions of trans-1-iodo-2-isothiocyanatocyclohexane with selenium nucleophiles have been investigated.Sodium hydrogenselenide gives a mixture of the 2-selone (2) and 2-thione (3) while lithium selenide gives mainly the 2-thione (3).With these reagents trans-1-iodo-2-isocyanatocyclohexane gives the corresponding selenazolidin-2-one (5).Treatment of 2-lithiobenzothiazole with N-phenylselenophthalimide or diphenyl diselenide gives 2-phenylselenobenzothiazole, while reaction of the sodium salt of selenobenzothiazole with alkyl or allyl halides affords high yields of 2-alkylseleno- and 2-allylselenobenzothiazoles, respectively.Treatment of 2-decylselenobenzothiazole with either hydrogen peroxide or m-chloroperbenzoic acid leads to low yields of the Pummerer rearrangement product (40). 2-Prop-2'-enylselenobenzothiazole can be used as a transfer reagent in palladium-catalysed allylation of diethyl malonate.Alternative routes to vic-iodoselenocyanates have been investigated.
- Cambie, Richard C.,Rutledge, Peter S.,Tan, Vivien Y. Y.,Woodgate, Paul D.
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p. 3655 - 3694
(2007/10/02)
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- Fluoride Ion Elimination-Addition Reactions. Synthesis of 2,2-Difluoroethenyl Phenyl Selenide and 2,2,2-Trifluoroethyl Phenyl Selenide
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2-Chloro-2,2-difluoroethyl phenyl selenide (1) reacts with KF and a catalytic amount of 18-crown-6 to give 2,2-difluoroethenyl phenyl selenide (3) and 2,2,2-trifluoroethyl phenyl selenide (4).The latter is formed by an elimination-addition sequence. 2-Bro
- Feiring, Andrew E.
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p. 1958 - 1961
(2007/10/02)
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- 1-(Trifluoromethyl)ethenyl Phenyl Selenide and 1-(Trifluoromethyl)ethenyl Phenyl Sulfide
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The title compounds were prepared by addition of phenylselenenyl chloride or phenylsulfenyl chloride to 3,3,3-trifluoropropene, followed by elimination of HCl.Both compounds react readily with nucleophiles, giving with ethyl acetoacetate novel 2-fluoro-4H-pyran derivatives.The selenium-substituted olefin reacted with n-butyllithium at selenium to give phenyl n-butyl selenide, while the corresponding sulfur-containig species underwent exclusive attack at the methylene terminus of the olefin.
- Feiring, Andrew E.
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p. 1962 - 1964
(2007/10/02)
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- A FACILE RING OPENING REACTION OF FURFURYL SELENIDES. HIGHLY EFFICIENT METHOD FOR DIENONES
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Treatment of furfuryl phenyl selenides with butyllithium or metallic lithium induces the facile ring opening reaction of their furan ring and the corresponding dienones are obtained in high yields.
- Kuwajima, Isao,Hoshino, Showay,Tanaka, Toshihiko,Shimizu, Makoto
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p. 3209 - 3212
(2007/10/02)
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