- Green preparation method of aryl diselenium ether type organic selenium compound
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The invention discloses an aryl diselenium ether compound synthesis method. The synthesis method comprises the following steps: taking the compound represented by the formula (I) as a reaction raw material, CuBr as a catalyst, KOH in the condition Se, a reducing agent, a disproportionation reaction, water or ethanol as a solvent, and 60 °C. After completion of the reaction, the obtained reaction solution is subjected to post-treatment (if ethanol is recovered as solvent) to obtain the aryl diselenoether compound represented by the formula (II), the yield is close 100%, the subsequent treatment is simple, and a complex separation and purification method is not needed to obtain a pure product. The solvent is recovered as a solvent such as ethanol. , It is preferable. The method is more green. Economy, high efficiency, environmental protection.
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Paragraph 0052-0056
(2021/11/14)
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- Lead optimization generates selenium-containing miconazole CYP51 inhibitors with improved pharmacological profile for the treatment of fungal infections
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A series of selenium-containing miconazole derivatives were identified as potent antifungal drugs in our previous study. Representative compound A03 (MIC = 0.01 μg/mL against C.alb. 5314) proved efficacious in inhibiting the growth of fungal pathogens. However, further study showed lead compound A03 exhibited potential hemolysis, significant cytotoxic effect and unfavorable metabolic stability and was therefore modified to overcome these drawbacks. In this article, the further optimization of selenium-containing miconazole derivatives resulted in the discovery of similarly potent compound B17 (MIC = 0.02 μg/mL against C.alb. 5314), exhibiting a superior pharmacological profile with decreased rate of metabolism, cytotoxic effect and hemolysis. Furthermore, compound B17 showed fungicidal activity against Candida albicans and significant effects on the treatment of resistant Candida albicans infections. Meanwhile, compound B17 not only could reduce the ergosterol biosynthesis pathway by inhibiting CYP51, but also inhibited biofilm formation. More importantly, compound B17 also shows promising in vivo efficacy after intraperitoneal injection and the PK study of compound B17 was evaluated. In addition, molecular docking studies provide a model for the interaction between the compound B17 and the CYP51 protein. Overall, we believe that these selenium-containing miconazole compounds can be further developed for the potential treatment of fungal infections.
- Xu, Hang,Yan, Zhong-zuo,Guo, Meng-bi,An, Ran,Wang, Xin,Zhang, Rui,Mou, Yan-hua,Hou, Zhuang,Guo, Chun
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- Nickel-Catalyzed Intramolecular Decarbonylative Coupling of Aryl Selenol Esters
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This report describes a method for Ni-catalyzed intramolecular decarbonylative coupling, which enables the conversion of areneselenol esters to diaryl selenides. The inexpensive and readily available catalyst can be employed under mild reaction conditions for the construction of structurally diverse diaryl selenides, including heterocyclic and natural product derivatives. (Figure presented.).
- Bai, Jin-Hua,Qi, Xiu-Juan,Sun, Wei,Yu, Tian-Yang,Xu, Peng-Fei
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supporting information
p. 2084 - 2088
(2021/03/01)
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- Rhodium-Catalyzed Enantioselective Hydroselenation of Heterobicyclic Alkenes
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A highly efficient Rh(I)/(S)-xyl-Binap catalytic system is developed for the asymmetric hydroselenation of various nonpolar olefins with diselenides. Under these mild reaction conditions, a wide range of heterobicyclic alkenes give selenol-incorporated adducts in excellent enantioselectivities (up to 97%) along with high yields (up to 96%) by overcoming self-promoted racemic hydroselenation. The strategy is also applied for kinetic resolution of unsymmetric oxabenzonorbornadiene.
- Li, Sifeng,Yang, Qingjing,Bian, Zhaoxiang,Wang, Jun
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supporting information
p. 2781 - 2785
(2020/03/30)
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- Trifluoromethylthiolative 1,2-difunctionalization of alkenes with diselenides and AgSCF3
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An efficient regioselective difunctionalization of alkenes via trifluoromethylthiolation has been accomplished employing diaryl diselenide and AgSCF3 in the presence of BF3·OEt2. Various substituted 1,2-dichalcogenated products having the SCF3 moiety were synthesized in good to excellent yields under mild conditions. The preliminary mechanistic investigation revealed the possible reaction pathway and unique combination of diselenide and AgSCF3 for successful transformation.
- Saravanan, Perumal,Anbarasan, Pazhamalai
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supporting information
p. 4639 - 4642
(2019/05/02)
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- Metal-Free ipso -Selenocyanation of Arylboronic Acids Using Malononitrile and Selenium Dioxide
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The first ipso -selenocyanation of arylboronic acids is achieved using selenium dioxide and malononitrile under mild conditions. The reaction is successful even without metal or base in DMSO. The major advantages of this new method are an easy set-up, excellent yields, and the use of odorless and inexpensive selenium reagents. Basic conditions subsequently afford new access to diaryldiselenides in good yields without isolating the organoselenocyanate intermediates.
- Broggi, Julie,Kosso, Anne Roly Obah,Redon, Sébastien,Vanelle, Patrice
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supporting information
p. 3758 - 3764
(2019/09/30)
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- One-pot preparation of (RSe)2CF2 and (RS)2CF2 compounds via insertion of TMSCF3-derived difluorocarbene into diselenides and disulfides
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A method for the first direct insertion of difluorcarbene, generated from TMSCF3, into diselenides and disulfides is disclosed, producing novel difluoromethyl diselenoacetals and difluoromethyl dithioacetals. The reaction conditions tolerate a range of synthetically useful and biologically relevant functional groups. The process is scalable, with two representative compounds prepared at a gram-scale in good yields, and it utilizes cheap and available reagents.
- Barrett, Colby,Krishnamurti, Vinayak,Oliveira, Artur Pratas,Prakash, G.K. Surya
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p. 4167 - 4173
(2019/04/30)
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- CuO nanoparticles-catalyzed a novel method to the synthesis of symmetrical diselenides from aryl halides: selenoamide as an organic Se-donor reagent
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A new method is reported for the synthesis of symmetrical diaryldiselenides from aryl halides using selenoamide as an organic Se-donor reagent in the presence of copper (II) oxide nanoparticles. CuO nanoparticles were found to be an efficient and inexpensive catalyst for ligand-free C-Se bond formation with a series of symmetrical diaryldiselenides obtained in good to excellent yield.
- Soleiman-Beigi, Mohammad,Yavari, Issa,Sadeghizadeh, Fatemeh
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p. 2239 - 2246
(2018/08/04)
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- Mechanistic Studies on the Anodic Functionalization of Alkenes Catalyzed by Diselenides
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Herein, we present a detailed kinetic and thermodynamic analysis of the anodic allylic esterification of alkenes as well as the bulk application of the anodic amination and esterification of nonactivated alkenes catalyzed by diselenides. The electrochemical study led to a comprehensive picture of the coupled electrochemical and chemical reaction steps. Cyclic voltammetry measurements are consistent with a bimolecular step after initial electrochemical 1e- oxidation of the diphenyl diselenide catalyst, 1a, and therefore we postulate a dimerization of the cation, which reacts very rapidly with the alkene, forming the addition product, i.e. the selenolactone 2a. Subsequent electrochemical oxidation of 2a occurs at a slightly higher potential than initial oxidation of 1a. The second oxidation is also followed by a bimolecular process and we hypothesize a dimerization of the cation, which finally eliminates 1a and protons in the rate-determining step, forming the product. Electrochemical analysis of various catalysts, i.e. nonsterically demanding diaryl diselenides with electron withdrawing and donating substituents, revealed that the oxidation potential of the catalyst and the intermediate can be readily tuned by the substituents, thus, prospectively allowing for a wide application of olefinic and nucleophilic substrates. The substituent pattern at the alkene has a smaller influence on the redox potential of the adduct. Controlled potential electrolysis experiments employing different nucleophiles proved that the reaction can be run electrochemically. The functionalization of unactivated alkenes with N- and O-nucleophiles was successfully demonstrated in several bulk electrolysis experiments, and the products were isolated in good yields.
- Wilken, Mona,Ortgies, Stefan,Breder, Alexander,Siewert, Inke
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p. 10901 - 10912
(2018/11/02)
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- Aerobic Allylation of Alcohols with Non-Activated Alkenes Enabled by Light-Driven Selenium-π-Acid Catalysis
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A new organocatalytic protocol for the aerobic dehydrogenative allylation of alcohols using non-activated alkenes as the allylating reagent and ambient air as the terminal oxidant is established. Mechanistically, the procedure relies on the interplay of a diselane and a photoredox catalyst by means of a light-induced electron transfer process. Under optimized conditions, a broad range of both cyclic and acyclic ethers is accessed with very high functional group tolerance and excellent regioselectivity.
- Rode, Katharina,Palomba, Martina,Ortgies, Stefan,Rieger, Rene,Breder, Alexander
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supporting information
p. 3875 - 3885
(2018/09/29)
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- Chain-Breaking Phenolic 2,3-Dihydrobenzo[b]selenophene Antioxidants: Proximity Effects and Regeneration Studies
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Phenolic 2,3-dihydrobenzo[b]selenophene antioxidants bearing an OH-group ortho (9), meta (10, 11) and para (8) to the Se were prepared by seleno-Claisen rearrangement/intramolecular hydroselenation. meta-Isomer (11) was studied by X-ray crystallography. The radical-trapping activity and regenerability of compounds 8–11 were evaluated using a two-phase system in which linoleic acid was undergoing peroxidation in the lipid phase while regeneration of the antioxidant by co-antioxidants (N-acetylcysteine, glutathione, dithiothreitol, ascorbic acid, tris(carboxyethyl)phosphine hydrochloride) was ongoing in the aqueous layer. Compound 9 quenched peroxyl radicals more efficiently than α-tocopherol. It also provided the most long-lasting antioxidant protection. With thiol co-antioxidants it could inhibit peroxidation for more than five-fold longer than the natural product. Regeneration was more efficient when the aqueous phase pH was slightly acidic. Since calculated O?H bond dissociation energies for 8–11 were substantially larger than for α-tocopherol, an antioxidant mechanism involving O-atom transfer from peroxyl to selenium was proposed. The resulting phenolic selenoxide/alkoxyl radical would then exchange a hydrogen atom in a solvent cage before antioxidant regeneration at the aqueous lipid interphase.
- Singh, Vijay P.,Yan, Jiajie,Poon, Jia-Fei,Gates, Paul J.,Butcher, Ray J.,Engman, Lars
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p. 15080 - 15088
(2017/10/17)
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- The direct synthesis of symmetrical disulfides and diselenides by metal-organic framework MOF-199 as an efficient heterogenous catalyst
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A highly crystalline porous copper-based metal-organic framework MOF-199 was synthesized, and characterized by several techniques, including XRD, EDX, SEM, and FT-IR. MOF-199 was used as an efficient catalyst for the one-pot and efficient synthesis of organic dichalcogenides from aryl halides (-OTs) and elemental sulfur and selenium in polyethylene glycols (PEGs). A variety of disulfides and diselenides can be obtained in good to excellent yields of up to 98% in a relatively short reaction time.
- Soleiman-Beigi, Mohammad,Yavari, Issa,Sadeghizadeh, Fatemeh
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p. 87564 - 87570
(2015/11/09)
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- α-Arylchalcogenation of acetone with diaryl dichalcogenide via metal-free oxidative C(sp3)-H bond functionalization
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Direct α-arylchalcogenation of acetone with diaryl dichalcogenides has been achieved by using a mixture of TBHP and DTBP oxidants at 120 °C without transition-metal catalyst via oxidative C(sp3)-H bond functionalization. The method exhibits good functional group tolerance and products were isolated in moderate to high yields.
- Yan, Guobing,Borah, Arun Jyoti,Wang, Lianggui,Pan, Zhangjin,Chen, Shuangshuang,Shen, Xuqian,Wu, Xiangmei
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supporting information
p. 4305 - 4307
(2015/06/22)
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- Efficient silver-catalyzed direct sulfenylation and selenylation of rich arenes
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An efficient protocol for silver/copper-cocatalyzed direct sulfenylation and selenylation of arenes with aryl disulfides and diselenides has been developed. This strategy exhibits excellent functional group tolerance and high regioselectivity. Mono sulfenylation and selenylation products can be exclusively achieved. This reaction provides a simple and practical route to the preparation of aryl sulfides and selenides. This journal is
- Yan, Guobing,Borah, Arun Jyoti,Wang, Lianggui
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supporting information
p. 9557 - 9561
(2015/02/19)
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- Microwave-assisted one-pot synthesis of symmetrical diselenides, ditellurides and disulfides from organoyl iodides and elemental chalcogen catalyzed by CuO nanoparticles
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In this study CuO nanoparticles were applied as a catalyst for CSe, CTe, and CS bond formation. The reaction was performed with organoyl iodides and elemental selenium, tellurium or sulfur under microwave irradiation in the presence of a base and solvent at 80 °C. This novel protocol allowed the synthesis of a variety of diselenides, ditellurides and disulfides in good to excellent yields in a very short reaction time.
- Botteselle, Giancarlo V.,Godoi, Marcelo,Galetto, Fabio Z.,Bettanin, Luana,Singh, Devender,Rodrigues, Oscar E.D.,Braga, Antonio L.
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p. 186 - 193
(2013/01/14)
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- Tertiary amine-based glutathione peroxidase mimics: Some insights into the role of steric and electronic effects on antioxidant activity
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In this work, several tertiary amine-based diaryl diselenides were synthesized and evaluated for their glutathione peroxidase (GPx)-like antioxidant activities using hydrogen peroxide, tert-butyl hydroperoxide and cumene hydroperoxide as substrates and thiophenol (PhSH) and glutathione (GSH) as co-substrates. A comparison of the GPx-like activity of 4-methoxy-substituted N,N-dialkylbenzylamine-based diselenides with that of the corresponding 6-methoxy-substituted compounds indicates that the activity highly depends on the position of the methoxy substituent. Although the methoxy group at 4- and 6-position alters the electronic properties of selenium, the substitution at the 6-position provides the required steric protection for some of the key intermediates in the catalytic cycle. A detailed experimental and theoretical investigation reveals that the 6-methoxy substituent prevents the undesired thiol exchange reactions at the selenium centers in the selenenyl sulfide intermediates. The 6-methoxy substituent also prevents the formation of seleninic and selenonic acids. When PhSH is used as the thiol co-substrate, the 4-methoxy-substituted diselenides exhibit GPx-like activity similar to that of the parent compounds as the 4-methoxy substituent does not block the selenium center in the selenenyl sulfide intermediates from thiol exchange reactions. In contrast, the 4-methoxy substituent significantly enhances the GPx-like activity of the diselenides when glutathione (GSH) is used as the co-substrate.
- Bhowmick, Debasish,Mugesh, Govindasamy
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p. 10550 - 10560,11
(2012/12/13)
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- Copper catalyzed/mediated synthetic methodology for ebselen and related isoselenazolones
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Scope of the copper catalyzed/mediated selenium-nitrogen coupling reaction has been studied for the synthesis of isoselenazolones. It is noticed that the 2-chloro, 2-bromo-, and 2-iodo-aryl amides substrates can be exploited in the selenium-nitrogen coupling reaction by employing 25-100 mol % of CuI/1,10-phenanthroline (L) and potassium carbonate as a base in DMF. Furthermore, electron rich 2-chloro-arylamides also underwent selenium-nitrogen coupling reaction to give biologically important selenium-nitrogen heterocycles. Also, copper-catalyzed selenium-nitrogen coupling reaction has been meticulously applied for the synthesis of diaryl diselenides having methoxy, amine, and amide functionality from respective aryl iodides in the presence of stoichiometric amount of succinimide as an external Se-N coupling partner.
- Balkrishna, Shah Jaimin,Bhakuni, Bhagat Singh,Kumar, Sangit
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experimental part
p. 9565 - 9575
(2011/12/15)
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- Studies on substituted aromatic diselenides as catalysts for selective alcohol oxidation using tert-butyl hydroperoxide
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We have investigated the Ph2Se2-catalysed oxidation of alcohols with tert-butyl hydroperoxide (TBHP) by using a variety of spectroscopic techniques and reaction calorimetry. We showed that the active oxidant is benzeneseleninic anhydride (BSA), formed by reaction of Ph 2Se2 with TBHP. The influence of aromatic substituents on the activity of a selection of nine aromatic diselenides involved in alcohol oxidations was studied. Calorimetric experiments showed that compounds that are activated more rapidly have higher initial activity in the catalytic oxidation of benzyl alcohol. An exception to this rule was observed when the diselenide contained a dimethylamino group in the ortho position, which can apparently compensate for its slow pre-activation by a special ortho effect. An aliphatic alcohol, 1-decanol was also used as a substrate. Besides diphenyl diselenide only three of the substituted diaryl diselenides studied showed reasonable activity after pre-activation with TBHP. Dimesityl diselenide displayed the highest activity and selectivity for the oxidation of 1-decanol. Specificity for a given aldehyde could be achieved by using an oxidant and substrate feed protocol. The oxidation steps from Ph2Se2 to benzeneseleninic anhydride, which is a gooddehydrogenation agent, have been elucidated by a combination of spectroscopic techniques, both in situ and ex situ. The oxidation potentials of derivatives of this anhydride have been investigated in the oxidation of 1-decanol.
- Van Der Toorn, John C.,Kemperman, Gerjan,Sheldon, Roger A.,Arends, Isabel W. C. E.
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experimental part
p. 4345 - 4352
(2011/09/15)
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- An efficient one-pot synthesis of symmetrical diselenides or ditellurides from halides with CuO nanopowder/Se0 or Te0/base
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(Equation Presented). A CuO nanopowder-catalyzed coupling reaction of aryl, alkyl, and heteroaryl iodides with elemental selenium and tellurium takes place in the presence of KOH at 90 °C in DMSO. A wide range of substituted symmetrical diselenides and ditellurides were afforded with good to excellent yields.
- Singh, Devender,Deobald, Anna M.,Camargo, Leandro R.S.,Tabarelli, Greice,Rodrigues, Oscar E.D.,Braga, Antonio L.
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supporting information; experimental part
p. 3288 - 3291
(2010/09/30)
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- ORGANOSELENIUM COMPOUNDS. V. SYNTHESIS OF ALLYLOXY- AND CYCLOHEXYLOXYDI(ARYLSELENO)METHANES
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Aryloxy- and cyclohexyloxydi(arylseleno)methanes were obtained by the reaction of dichloromethyl aryl and dichloromethyl cyclohexyl ethers with arylselenomagnesium bromides or sodium areneselenolates.
- Lapkin, I. I.,Nedugov, A. N.,Bulatov, P. O.,Pavlova, N. N.,Gartman, G. A.,Novichkova, A. S.
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- STUDIES ON LONG-RANGE COUPLINGS BETWEEN 77Se AND 13C IN SOME ARYL SELENIDES, DICHLORIDES, AND SELENOXIDES. THE INVERSE EFFECT ON COUPLINGS IN THE SELENOXIDE FORMATION.
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Long-range coupling constants between **7**7Se and **1**3C in selenoanisole, diphenyl selenide, diphenyl diselenide, and their 2-mono- and 2,2 prime -disubstituted derivatives, selenoxanthone, selenanthrene, dichlorides, and selenoxides were measured to disclose predominant factors governing the magnitude of the coupling. Extraordinary large values for two- and three-bond couplings are found in selenoxanthone. Three factors are operative: the orientational effect, the coordination number, and the effect of ring formation. The last factor accompanies a stronger inverse effect on the coupling of selenoxides than on that of selenides.
- Nakanishi,Ikeda
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p. 1661 - 1664
(2007/10/02)
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- NEW SYNTHETIC METHODS : SODIUM ALKANECHALCOGENATES AS DEMETHYLATING AGENTS. SCOPE, LIMITATION AND NEW ONE-POT SYNTHESIS OF DIARYLDISELENIDES.
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Sodium alkanechalcogenates (S, Se) cleave the alkylarylchalcogenides (O, S, Se).The versatility of such reagents is developed and applied to a new synthesis of diaryldiselenides.
- Evers, Michel,Christiaens, Leon
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p. 377 - 380
(2007/10/02)
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