- Iodosobenzene-Mediated Three-Component Selenofunctionalization of Olefins
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A three-component reaction of olefin, diselenide and water, alcohols, phenol, carboxylic acid, or amine by a commercially available hypervalent iodine(III) reagent, PhIO, was developed. This method provides access to a wide range of vicinally functionalized selenoderivatives under ambient conditions with mostly excellent yields and high diastereoselectivity. The developed reaction displays high levels of functional group compatibility and is suitable for the late-stage functionalization of styrene-functionalized biomolecules. Preliminary investigations on the mechanism of the reaction are also presented.
- Liang, Zhi-Peng,Yi, Wei,Wang, Peng-Fei,Liu, Gong-Qing,Ling, Yong
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p. 5292 - 5304
(2021/04/06)
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- Automated Electrochemical Selenenylations
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Integrated electrochemical reactors in automated flow systems were utilised for selenenylation reactions. The automation allowed multiple electrochemical reactions of a programmed sequence to be performed in a fully autonomous way. Many functionalised selenenylated products were synthesised in short reaction times in good to high yields.
- Amri, Nasser,Wirth, Thomas
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supporting information
p. 1751 - 1761
(2020/06/08)
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- A novel and efficient alkoxylselenenylation of alkenes
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A novel and efficient alkoxylselenenylation from alkenes, diselenides, and alcohols mediated by iodine is developed, with which a series of β-alkoxy selenides are synthesized. In this procedure, firstly, I2 reacts with diselenide to form in situ the active electrophilic selenium species RSeI, then following an electrophilic addition of it to alkenes provides β-alkoxy selenides with high regioselectivity and in good yields. This new method for achieving β-alkoxy selenides has some advantages over other methods such as using available and cheap iodine as the oxidizing species at room temperature, which makes this reaction has milder reaction conditions and simpler procedure.
- Fang, Yingguo,Yan, Jie
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p. 1039 - 1045
(2020/01/08)
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- Efficient Protocol for Synthesis of β-Hydroxy(alkoxy)selenides via Electrochemical Iodide-Catalyzed Oxyselenation of Styrene Derivatives with Dialkyl(aryl)diselenides
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An efficient protocol for the synthesis of β-hydroxy(alkoxy)selenides was developed through the electrochemical iodide-catalyzed oxyselenation of styrene derivatives with dialkyl(aryl)diselenides under mild reaction conditions. Mechanistic studies showed that the cation I+ is involved during the whole process, and accelerates the formation of seleniranium ion via substitution and addition reaction with dialkyl(aryl)diselenides and styrene derivatives. The corresponding products are formed in good to excellent yields. This electrochemical oxyselenation provides an efficient strategy for difunctionalization of alkenes.
- Chen, Jinyang,Mei, Lan,Wang, Haiying,Hu, Li,Sun, Xiaorui,Shi, Jianwei,Li, Qiang
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p. 1230 - 1234
(2019/09/17)
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- Electrochemical Aminoselenation and Oxyselenation of Styrenes with Hydrogen Evolution
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The use of additive-free conditions is an ideal approach to prepare organoselenium reagents from readily available unsaturated substrates. Thus, we report the electro-induced aminoselenation and oxyselenation of styrenes without any acids or oxidants as additives. This transformation is compatible with various functional groups, which leads to vicinal difunctionalized organoselenium compounds. Our strategy improves the potential of this protocol for use in the pharmaceutical industry. Based upon the preliminary mechanism studies, we propose two possible pathways.
- Sun, Li,Yuan, Yong,Yao, Min,Wang, Han,Wang, Daoxin,Gao, Meng,Chen, Yi-Hung,Lei, Aiwen
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supporting information
p. 1297 - 1300
(2019/02/19)
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- Visible light-promoted, iodine-catalyzed selenoalkoxylation of olefins with diselenides and alcohols in the presence of hydrogen peroxide/air oxidant: an efficient access to α-alkoxyl selenides
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Under iodine-catalyzed and visible light-irradiated aerobic conditions, selenoalkoxylation of olefins with diselenides and alcohols can be efficiently achieved to afford the useful α-alkoxyl selenides in the presence of only 0.5 equiv. of H2O2. Controlling the sub-stoichiometric H2O2 amount is crucial to avoid the non-selective over-oxidation of the diselenides that leads to the ineffective hyper-valent selenium compounds. Meanwhile, under visible light irradiation, the green, safe, and low-cost air can work as a supplemental mild oxidant in the reaction to ensure selective oxidation of the diselenides, full conversion of the reactants, and ultimately good yield of the products.
- Liu, Mingxuan,Li, Yiming,Yu, Lei,Xu, Qing,Jiang, Xuefeng
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p. 294 - 299
(2018/01/04)
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- Selenomethoxylation of Alkenes Promoted by Oxone
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We describe herein an alternative method for the selenomethoxylation of unactivated alkenes using Oxone as a stoichiometric oxidant. The electrophilic species of selenium were easily generated in situ by the reaction of diorganyl diselenides with Oxone. By this efficient and simple approach, β-methoxy-selenides were obtained in moderate to excellent yields at room temperature in an open flask, starting from alkenes by using methanol as both nucleophile and solvent. When a mixture of H2O/CH3CN was employed as the solvent, β-hydroxy-selenides were selectively obtained under mild conditions.
- Perin, Gelson,Santoni, Paolo,Barcellos, Angelita M.,Nobre, Patrick C.,Jacob, Raquel G.,Lenard?o, Eder J.,Santi, Claudio
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p. 1224 - 1229
(2018/03/21)
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- Acidic hierarchical zeolite ZSM-5 supported Ru catalyst with high activity and selectivity in the seleno-functionalization of alkenes
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The acidic hierarchical zeolite ZSM-5 (HZSM-5-H) was synthesized for the preparation of a supported Ru catalyst (Ru/HZSM-5-H). The obtained Ru/HZSM-5-H catalyst shows high activity and product selectivity in the seleno-functionalization of alkenes compared to γ-Al2O3, basic ETS-10 and acidic microporous zeolite ZSM-5 supported Ru catalysts (Ru/γ-Al2O3, Ru/ETS-10 and Ru/HZSM-5, respectively), as well as a homogeneous RuCl3 catalyst. The relatively strong acidic sites in Ru/HZSM-5-H could benefit the adsorption of styrenes and the activation of the CC bond. Meanwhile, Ru4+ in Ru/HZSM-5-H could facilitate the formation of electrophilic selenium species as compared to Ru0 species. In addition, the Ru/HZSM-5-M catalyst exhibits broad substrate compatibility in the difunctionalization of alkenes.
- Dong, Hai,Zhang, Lei,Fang, Zhongxue,Fu, Wenqian,Tang, Ting,Feng, Yu,Tang, Tiandi
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p. 22008 - 22016
(2017/07/10)
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- Catalytic chalcogenylation under greener conditions: A solvent-free sulfur- and seleno-functionalization of olefins via I2/DMSO oxidant system
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Herein, we report a solvent- and metal-free methodology for the alkoxy-chalcogenylation of styrenes, using molecular iodine as a catalyst, DMSO as a stoichiometric oxidant, and different nucleophiles under microwave irradiation. This eco-friendly approach afforded the desired products in good to excellent yields in only 10 min. In addition, using the same protocol, we carried out the cyclization reaction of relevant molecules, such as lapachol derivatives.
- Vieira, André A.,Azeredo, Juliano B.,Godoi, Marcelo,Santi, Claudio,Da Silva Júnior, Eufranio N.,Braga, Antonio L.
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p. 2120 - 2127
(2015/05/12)
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- N-Phenylselenosaccharin (NPSSac): a new electrophilic selenium-containing reagent
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A new reagent N-phenylselenosaccharin (NPSSac) was simply prepared and used as a source of the electrophilic phenylselenyl group. This relatively stable new compound was able to react with a series of electron rich organic molecules like alkenes in the pr
- Tingoli, Marco,Diana, Rosita,Panunzi, Barbara
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p. 7529 - 7531
(2007/10/03)
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- Convenient one-pot synthesis of vinyl ethers from phenyl 2-hydroxyalkyl selenides
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Vinyl ethers were prepared with good yields in a one-pot, two-step transformation by O-alkylation reaction of phenyl 2-hydroxyalkyl selenides with primary or secondary organic halides followed by oxidation elimination with 30% hydrogen peroxide. Copyright
- Sheng, Shou-Ri,Luo, Hai-Rong,Sun, Wu-Kang,Liu, Xiao-Ling,Xin, Qin,Wang, Qiu-Ying
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p. 2839 - 2845
(2007/10/03)
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- A novel role of zeolite NaY in the thermal reaction of alkyl aryl selenoxides in its supercages
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Thermal reaction of alkyl aryl selenoxides in the presence of water or methanol in the supercage of zeolite NaY gave β-hydroxy- or β-methoxyalkyl aryl selenides, respectively, and NaY played a novel role to stabilize reactive ArSeOH and to separate an anion of -OH from a carbonium ion which was simultaneously present with the -OH in a supercage.
- Zhang, Wanxuan,Yu, Haitao,Gao, Yu,Meng, Jiben,Matsuura, Teruo
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p. 498 - 499
(2007/10/03)
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- Oxidation of diphenyl diselenide with 2,3-dichloro-5,6-dicyanobenzoquinone (DDQ). A new method for the electrophilic phenylselenenylation of alkenes under mild conditions
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The oxidation of diphenyl diselenide with 2,3-dichloro-5,6-dicyanobenzoquinone (DDQ) represents a convenient mild method to produce a strongly electrophilic phenylselenium reagent. Clean phenylseleno methoxylations and hydroxylations of alkenes containing different types of functional groups can be effected by working in methanol or in acetonitrile and water, respectively. This new electrophilic reagent can also be employed to promote efficient cyclization reactions of alkenols to tetrahydrofurans or of alkenoic acids to lactones.
- Tiecco,Testaferri,Temperini,Bagnoli,Marini,Santi
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p. 1767 - 1771
(2007/10/03)
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- Oxidation of Diphenyl Diselenide with Ceric Ammonium Nitrate: a Novel Route for Functionalization of Olefins
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Alkenes were reacted with diphenyl diselenide in presence of ceric ammonium nitrate in methanol, affording β-methoxyalkyl phenyl selenides in good yields.
- Bosman, Cesare,D'Annibale, Andrea,Resta, Stefano,Trogolo, Corrado
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p. 6525 - 6528
(2007/10/02)
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- Oxidative Cleavage of Diselenide by m-Nitrobenzenesulfonyl Peroxide. Novel Method for the Electrophilic Benzeneselenenylations of Olefins and Aromatic Rings
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Diphenyl diselenide was found to be readily converted into benzeneselenenyl-m-nitrobenzenesulfonate (PhSeOSO2C6H4NO2-m) by treating with m-nitrobenzenesulfonyl peroxide.When the selenenyl sulfonate thus formed was allowed to react in situ with olefins, such as cyclohexene, 1-octene, or styrene, in the presence of various nucleophiles, the adducts of benzeneselenenyl group and a nucleophile were obtained.As the nucleophiles water, methanol, acetic acid, phenol, and anisole could be employed; oxyselenenylated : R=H, Me, Ac, and Ph) and arylselenenylated : R=H and Me) adducts were afforded.Phenol gave oxyselenenylated products in cyclohexene or 1-octene and arylselenenylated products in styrene.Efficient intramolecular cyclizations of unsaturated alcohols and carboxylic acids were similarly performed by the selenenyl sulfonate to afford corresponding benzeneselenenylated cyclic ethers and lactones.The selenenyl sulfonate was also found to be a highly reactive benzeneselenenylating reagent for aromatic rings, such as anisole, phenol, acetanilide, toluene, and benzene.
- Yoshida, Masato,Sasage, Shuichi,Kawamura, Kyoko,Suzuki, Takashi,Kamigata, Nobumasa
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p. 416 - 422
(2007/10/02)
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- Selenium-Catalyzed Conversion of Methyl Ketones into α-Keto Acetals
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The reaction of methyl ketones with catalytic amounts of diphenyl diselenide and an excess of ammonium peroxydisulfate in methanol proceeds smoothly to afford α-keto acetals in good yield.In some cases reaction yields were increased by using stoichiometri
- Tiecco, M.,Testaferri, L.,Tingoli, M.,Bartoli, D.
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p. 4523 - 4528
(2007/10/02)
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- Acetoxyselenenylation of Olefins for the Preparation of Vinylic and Allylic Acetates
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Terminal and 1,2-disubstituted olefins were irreversibly acetoxyselenenylated by treatment with PhSeBr in an acetate buffer solution.Styrene derivatives yielded only Markovnikov adducts whereas simple terminal olefins and olefins containing an allylic oxygen substituent (acyloxy or aryloxy group) afforded significant amounts (50-85percent) of the anti-Markovnikov isomer.The product mixtures were isomerized to contain 90-97percent of the Markovnikov products by treatment with a catalytic amount (6-41percent) of BF3*OEt2 in chloroform.Oxidation (SO2Cl2/hydrolysis or MCPBA) of the isomerized products and selenoxide elimination at elevated temperature toward the acetoxy group afforded enol acetates in fair yields.The selenoxides of the anti-Markovnikov isomers (unisomerized mixtures) spontaneously eliminated, in the presence of the selenoxides of the Markovnikov isomer, to give allylic acetates in good yields at ambient temperature.
- Engman, Lars
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p. 884 - 890
(2007/10/02)
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- THE REACTION O DIPHENYL DISELENIDE WITH PEROXYDISULPHATE IONS IN METHANOL A CONVENIENT PROCEDURE TO EECT THE METHOXYSELENENYLATION O ALKENES
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Methoxyselenenylation of several alkenes was efected, in one step, by oxidation of diphenyl diselenide with ammonium peroxydisulphate in methanol.
- Tiecco, M.,Testaerri, L.,Tingoli, M.,Chianelli, D.,Bartoli, D.
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p. 1417 - 1420
(2007/10/02)
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- Novel Method for Electrophilic Selenenylation Using Diselenide with Nitrobenzenesulfonyl Peroxide
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Diphenyl diselenide could be readily converted into cationic selenenylating reagent by treating with m-nitrobenzenesulfonyl peroxide, and the intermediate was reacted with olefins in the presence of methanol, phenol, or electorn-rich benzenes in one pot to afford methoxy-, phenoxy-, or arylselenenylated compounds, respectively.
- Yoshida, Masato,Satoh, Naomi,Kamigata, Nobumasa
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p. 1433 - 1436
(2007/10/02)
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- METHOXYCHLORINATION AND DIMETHOXYLATION OF ALKENES. THE REACTIONS OF SUBSTITUTED STYRENES WITH PHENYLSELENENYL CHLORIDE IN METHANOL
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The addition of PhSeCl to α- and β-substituted styrenes in methanol is regio- and stereospecific and affords the products of methoxyselenenylation.These compounds further react with PhSeCl to give the deselenenylation products.In the case of α-substituted styrenes, 1-methoxy, 2-chloroalkanes are produced, whereas with β-substituted styrenes the major reaction products are the 1,2-dimethoxyalkanes and the 2,2-dimethoxyalkanes in which phenyl migration has occured.It is shown that these reactions proceed through the intermediate formation of the alkyl phenylselenium dichlorides, PhCR(OMe)CHR1SeCl2Ph, which evolve with different mechanisms depending on the structure of the starting alkenes.
- Tiecco, Marcello,Testaferri, Lorenzo,Tingoli, Marco,Chianelli, Donatella,Bartoli, Donatella
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p. 2261 - 2272
(2007/10/02)
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- Regioselective Oxyselenenylation
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The regioselective oxyselenenylation of terminal olefins or cycloalkenes was achieved via olefin oxymercuration and subsequent radical substitution by selenenylating reagent such as S-benzoyl Se-phenyl selenosulfide, diphenyl diselenide, or phenylselenocy
- Toru, Takeshi,Yamada, Yoshio,Maekawa, Eturo,Ueno, Yoshio
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p. 1827 - 1830
(2007/10/02)
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- FORMATION AND REACTIVITY OF THE ADDITION PRODUCTS OF ALKOXIDES AND THIOLATE ANIONS TO VINYL SELENONES
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Vinyl selenones react with sodium methanethiolate in methanol to give the product of conjugate addition and subsequent displacement of the selenonyl group.On the contrary, the same reaction carried out with alkoxide anions affords the conjugate addition products in excellent yields.These β-alkoxy alkyl phenyl selenones are stable compounds which can react in several ways with loss of the selenonyl group.Their reactions with MeONa or MeSNa have been investigated both in MeOH and in DMF.The products observed derive from substitution and elimination processes as well as from retro Michael reactions followed by nucleophilic substitution of the vinyl selenone thus generated.These results indicate that the ArSeO2 is a strong electron attracting group with peculiar properties.Beside making acidic the α-hydrogen atoms it activates the carbon-carbon double bond towards the addition of anionic reagents and it acts as a good leaving group in nucleophilic substitution, both aliphatic and vinylic, and in elimination reactions.The appropriate choice of the reagent and of the solvent allows to direct the reaction towards the desired products.Useful synthetic applications of these reactions are presented.
- Tiecco, Marcello,Chianelli, Donatella,Tingoli, Marco,Testaferri, Lorenzo,Bartoli, Donatella
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p. 4897 - 4906
(2007/10/02)
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- THE ELECTROPHILIC ADDITION OF SELENENYL THIOCYANATES TO OLEFINS
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Benzeneselenenyl thiocyanate in methanol reacts with olefins to give adducts; kinetic data for attack upon styrenes are presented.
- Parr, W. J. E.,Crafts, R. C.
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p. 1371 - 1372
(2007/10/02)
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- A halide ion promoted electrochemical oxyselenenylation of olefins
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A novel electrolytic transformation of olefins 1 into oxyselenides 2 has been performed in high yields and high regioselectivities by elctrolyzing olefins in protic solvents (MeOH, AcOH, H2O-MeCN) containing Et4NX (X = Cl, Br, I) and diphenyl diselenide using platinum foils.
- Torii, Sigeru,Uneyama, Kenji,Ono, Michio
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p. 2741 - 2744
(2007/10/02)
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- Facile Oxyselenation of Olefins in the Presence of Copper(II) or Copper(I) Chloride as Catalyst
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Treatment of olefinic hydrocarbons with phenyl selenocyanate in alcohol in the presence of copper(II) or copper(I) chloride affords β-alkoxyalkyl phenyl selenide in good yield.Similar reactions in aqueous tetrahydrofuran or acetic acid-chloroform give the corresponding selenide.The reaction is trans stereospecific in the cases of trans-2-butene, cis-2-butene, and cyclohexene and regiospecific in the cases of styrene, acrylaldehyde, crotonaldehyde, and vinylacetate, respectively.The reaction proceeds even with a catalytic amount of copper(II) chloride.Of the various transition-metal salts examined, nickel(II) halides are similar to copper(II) or copper(I) halides as catalyst; the chlorides of Cr(III) and Co(II) are moderately effective, while the chlorides of Mn(II), Fe(III), Fe(II), Zn(II), Ag(I), Cd(II), Hg(II), Hg(I), Tl(III), and Tl(I) are almost ineffective.The use of the pyridine complex of copper or nickel halides suppresses the reaction.The reaction is presumed to proceed via (i) the polarization of the Se-CN bond by coordination of the effective metal salt to the cyano group and (ii) a nucleophilic attack of olefin on the polarized selenium.The substituent parameters of phenylseleno and selenocyanato groups for 13C NMR have been found to be +13 and +15 to 16 ppm for the α carbon and +6 and +6 to 7 ppm for the β carbon, respectively.
- Toshimitsu, Akio,Aoai, Toshiaki,Uemura, Sakae,Okano, Masaya
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p. 1953 - 1958
(2007/10/02)
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