- Kinetic Study of the Pyridine-Catalyzed Selenolactonization of 4-Pentenoic Acid
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Abstract: The kinetics and mechanism of the pyridine-catalyzed cyclofunctionalization of 4-pentenoic acid by means of PhSeX (X = Cl, Br) have been investigated spectrophotometrically, under pseudo-first order reaction conditions. The influence of the reac
- Kosti?, Marina D.,Mihajlovi?, Kristina,Divac, Vera M.
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- Time-economical synthesis of selenofunctionalized heterocycles via I2O5-mediated selenylative heterocyclization
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A time-economical and robust synthesis of various selenofunctionalized heterocycles was accomplished via I2O5-mediated selenocyclizations of olefins with diselenides. Using this method, 116 selenomethyl-substituted heterocycles were
- Zhou, Chen-Fan,Zhang, Yun-Qian,Ling, Yong,Ming, Liang,Xi, Xia,Liu, Gong-Qing,Zhang, Yanan
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supporting information
p. 420 - 426
(2022/01/20)
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- Preparation of selenofunctionalized heterocycles via iodosobenzene-mediated intramolecular selenocyclizations of olefins with diselenides
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An intramolecular selenocyclizations of olefins mediated by a commercially available hypervalent iodine(III) reagent, PhIO, was developed. This method provided access to a wide range of selenenylated heterocycles under ambient conditions. The striking advantages of this protocol over all previous methods include mild reaction conditions, easy operation, good yields, high levels of functional group compatibility, large–scale application and suitability for the late-stage functionalization of complex molecules of biological importance.
- Wang, Peng-Fei,Yi, Wei,Ling, Yong,Ming, Liang,Liu, Gong-Qing,Zhao, Yu
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supporting information
p. 2587 - 2591
(2021/03/15)
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- Synthesis, characterization and biological studies of organoselenium trans-palladium(II) complexes
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Background: Over the years, transition metal complexes have exhibited significant antimicrobial and antitumor activity. It all started with cisplatin discovery, but due to the large number of side effects it shows, there is a growing need to find a new me
- Bogojeski, Jovana,Divac, Vera,Canovi?, Predrag,Kosti?, Marina,Mihailovi?, Kristina,Milivojevi?, Nevena,Mladenovi?, Katarina,Petrovi?, Angelina,Popovska Jovici?, Biljana,Radojevi?, Ivana,Rakovi?, Ivana,Zivanovi?, Marko
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p. 1007 - 1022
(2021/11/30)
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- Electrochemical Difunctionalization of Olefines: Access to Selenomethyl-Substituted Cyclic Ethers or Lactones
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A metal- and oxidant-free electrochemical method for preparing selenomethyl-substituted cyclic ethers or lactones via difunctionalization of olefines is presented. A series of selenomethyl-substituted cyclic ethers, particularly 9- and 11- membered, selen
- Meng, Xiu-Jin,Zhong, Ping-Fu,Wang, Yu-Mei,Wang, Heng-Shan,Tang, Hai-Tao,Pan, Ying-Ming
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supporting information
p. 506 - 511
(2019/12/24)
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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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- Preparation of Heterocycles via Visible-Light-Driven Aerobic Selenation of Olefins with Diselenides
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The aerobic dehydrogenative cyclization of alkenes with easily accessible diselenides facilitated by visible light is reported. Notably, the features of this transition-metal-free protocol are pronounced efficiency and practicality, good functional group
- Zhang, Qing-Bao,Yuan, Pan-Feng,Kai, Liang-Lin,Liu, Kai,Ban, Yong-Liang,Wang, Xue-Yang,Wu, Li-Zhu,Liu, Qiang
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supporting information
p. 885 - 889
(2019/02/14)
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- A mild and efficient procedure for alkenols oxyselenocyclization by using ionic liquids
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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 ab
- Kosti?, Marina,Verdía, Pedro,Fernández-Stefanuto, Verónica,Puchta, Ralph,Tojo, Emilia
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supporting information
(2019/01/08)
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- Iodine-mediated acyloxyselenenylation of alkenes
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In the presence of I2, an acyloxyselenenylation of alkenes with diselenides and carboxylic acids is developed. This metal-free iodine-mediated acyloxyselenenylation proceeds efficiently under mild reaction conditions, affording a series of 2-acyloxy-1-selenides with high regioselectivity and in moderate to good yields.
- Wang, Xiaolong,Wang, Junxing,Li, Hongjie,Yan, Jie,Yang, Zhenping
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p. 2745 - 2752
(2018/08/23)
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- Ammonium Iodide Catalyzed Selenolactonization of Unsaturated Acids
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A convenient procedure is developed for the preparation of selenolactones from unsaturated acids and diselenides using a catalytic amount of ammonium iodide in combination with m-chloroperoxybenzoic acid as the oxidant. This catalytic ring-closing method
- Shi, Hongwei,Yu, Chen,Zhu, Min,Yan, Jie
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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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- Visible-light-promoted selenofunctionalization of alkenes
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A visible-light-promoted method for the selenofunctionalization (and tellurofunctionalization) of alkenes has been developed. This method obviates the prepreparation of moisture-sensitive chalcogen electrophiles. The experimental setup is simple, and supe
- Conner, Elizabeth S.,Crocker, Katherine E.,Fernando, Ranelka G.,Fronczek, Frank R.,Stanley, George G.,Ragains, Justin R.
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supporting information
p. 5558 - 5561
(2013/11/19)
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- Synthesis of chiral 1,5-disubstituted pyrrolidinones via electrophile-induced cyclization of 2-(3-butenyl)oxazolines derived from (1R,2S)- and (1S,2R)-norephedrine
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Starting from (1R,2S)- and (1S,2R)-norephedrine, enantiomers of the corresponding 2-(3-butenyl)oxazolines were prepared in a two-step process. The cyclization of the intermediate alkenylamides with phenylselenyl bromide afforded cyclic imidates instead of the expected pyrrolidinones. The electrophile-induced cyclizations of 2-alkenyloxazolines with bromine or iodine produced diastereomeric mixtures of chiral 1,5-disubstituted pyrrolidinones. The ring closure of the all-cis (1R,2S,5R)-diastereomer 7 with NaH resulted in the tetrahydropyrrolo[2,1-b]oxazol-5-one derivative 18, which was alternatively prepared by the cyclocondensation of (1R,2S)-norephedrine with levulinic acid.
- Kanizsai, Ivan,Szakonyi, Zsolt,Sillanpaeae, Reijo,D'hooghe, Matthias,Kimpe, Norbert De,Fueloep, Ferenc
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p. 2857 - 2863
(2007/10/03)
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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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- Enzymatic Resolution of 5-Phenylselanyltetrahydro-2-furanone. Enantioselective Preparation of (R) and (S)-γ-Valerolactone
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Lipase-catalyzed lactonization of (2) provides both (R) and (S) enantiomers of 5-phenylselenyltetrahydro-2-furanone (1) in good enantiomeric excess. The kinetic resolution was examined using PPL (Porcine pancreatic lipase), PSL (Amano PS, Pseudomonas sp. lipase), MML (Mucor miehei lipase), CRL (Candida rugosa lipase), CAL-B (Candida Antarctica lipase, type B) and Novozym 435 (immobilized C. antarctica lipase type B) in different solvents. A tributyltin hydride reduction of enantiomerically enriched 1 gave both (R) and (S) enantiomers of S-4-pentanolide (γ-valerolactone).
- Clososki, Giuliano C.,Costa, Carlos E.,Missio, Lauri J.,Cass, Quezia B.,Comasseto, Joao V.
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p. 817 - 828
(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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- Selective intramolecular oxyselenenylation of olefinic alcohols and carboxylic acids by using organic cyanoselenides in the presence of metal triflates
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The reagent, ArSeCN - M(OTf)(n), is prepared from equimolar amounts of an aromatic selenocyanate and metal trifluoromethanesulfonate. It reacts with unsaturated alcohols and carboxylic acids to give cyclic ethers and lactones, respectively. Depending on c
- Murata, Shizuaki,Suzuki, Chisato,Inoue, Hirofumi,Andoh, Yukihiro,Hayashi, Yoshihiro,Suzuki, Toshiyasu
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p. 621 - 632
(2007/10/03)
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- Iodosobenzene diacetate and diphenyl diselenide: An electrophilic selenenylating agent of double bonds
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Phenylseleno-acetoxylation, hydroxylation, etherification and lactonization products are obtained in good yields from the reaction of alkenes with diphenyl diselenide and iodosobenzene diacetate, in acetonitrile.
- Tingoli, Marco,Tiecco, Marcello,Testaferri, Lorenzo,Temperini, Andrea
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p. 1769 - 1778
(2007/10/03)
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- The Binary Reagent PhSeSePh-CuOTf: a Useful Phenylselenylating Agent
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The binary reagent PhSeSePh-CuOTf has been found to be useful for the conversion of alkynyltrimethylsilanes into 1-phenylselenoalk-1-ynes as well as for phenylselenolactonization and phenylselenoetherification.
- Miyachi, Nobuhide,Satoh, Hisao,Shibasaki, Masakatsu
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p. 2049 - 2050
(2007/10/02)
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- Electrochemical cyclization of unsaturated hydroxy compounds. Phenylselenoetherification and phenylselenolactonization
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Phenylselenoetherification and phenylselenolactonization were performed in one step by electrolysis of unsaturated alcohols or carboxylic acids and diphenyl diselenide in organic solvent containing halide ions as mediators.
- Vukicevic,Konstantinovic,Mihailovic
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p. 859 - 865
(2007/10/02)
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- Formation and Electrophilic Reactions of Benzeneselenenyl p-Toluenesulfonate. Perparation and Properties of Addition Products with Acetylenes
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Benzeneselenenyl p-toluenesulfonate (1) was generated in situ by the reaction of silver p-toluenesulfonate with benzeneselenenyl chloride in acetonitrile.The reagent reacted with acetylenes by electrophilic 1,2-addition to afford the β-(phenylseleno)vinyl p-toluenesulfonates 2-12, generally in high yield.The latter were formed preferentially by anti addition, but with poor regioselectivity, unless a strongly orienting group (e.g., phenyl) was present.Selenenyl sulfonate 1 was also unexpectedly produced via radical pathways by heating p-toluenesulfonic acid with AIBN in the presence of diphenyl diselenide, or from the pyrolysis of sulfinyl sulfone 15 with the diselenide.The regioisomeric adducts 3 and 4 were prepared from 1 and 1-decyne, and both underwent elimination with potassium tert-butoxide to afford the acetylenic selenide 19 initially, which isomerized to a 6:1 mixture of the propargylic and allenic selenides 20 and 21 upon further equilibration.A Fritsch-Buttenberg-Wiechell rearrangement is proposed for the elimination of 4.The syn elimination of the selenoxide of 4 required forcing conditions and afforded only ca. 20percent of the corresponding allenic sulfonate 22.The electrophile 1 induced the efficient cyclization of 5-hexen-1-ol and 4-pentenoic acid to the corresponding pyran 24 and lactone 25, respectively.It failed to cyclize alkynols, but afforded the lactones 28 and 29 from 4-pentynoic acid in low yield.
- Back, Thomas G.,Muralidharan, K. Raman
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p. 2781 - 2787
(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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- Ring-Closure Reactions Initiated by the Peroxydisulfate Ion Oxidation of Diphenyl Diselenide
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The oxidation of diphenyl diselenide with ammonium peroxydisulfate proceeded cleanly to afford phenylselenium cations and sulfate anions.This is a very simple and efficient method to produce phenylselenium cations in the absence of nucleophilic counterions.This reaction was employed to effect selenium-induced ring closure reactions starting from alkenes containing internal nucleophiles.Thus, unsaturated alcohols and amides, β-diketones and β-keto esters gave the products of phenylselenoetherification.The same process occurred with dienes and unsaturated ketones when the reaction was carried out in the presence of water or methanol, respectively.Unsaturated acids, esters, and imides afforded the phenylselenolactonization products.
- Tiecco, M.,Testaferri, L.,Tingoli, M.,Bartoli, D.,Balducci, R.
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p. 429 - 434
(2007/10/02)
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- PHENYLSELENO-LACTONIZATION OF OLEFINIC NITRILES PROMOTED BY PEROXYDISULPHATE ION OXIDATION OF DIPHENYL DISELENIDE
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The oxidation of diphenyl diselenide with ammonium peroxydisulphate is a very simple and efficient method to produce phenylselenium cations in the absence of nucleophilic counter ions.The reaction carried out in the presence of an olefin, in acetonitrile
- Tiecco, Marcello,Testaferri, Lorenzo,Tingoli, Marco,Bartoli, Donatella
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p. 6819 - 6832
(2007/10/02)
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- ELECTROCHEMICAL CYCLIZATION OF UNSATURATED HYDROXY COMPOUNDS. PART II. PHENYLSELENOLACTONIZATION
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Phenylselenolactonization was performed, in one step, by electrolysis of Δ4- and Δ5-unsaturated carboxylic acids and diphenyl diselenide in methanol containing ammonium bromide.
- Konstantinovic, S.,Vukicevic, R.,Mihailovic, M. Lj.
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p. 6511 - 6512
(2007/10/02)
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- Stereoselective Selenolactonization by Superelectrophilic Benzeneselenenyl Triflate
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Benzeneselenenyl triflate is prepared from benzeneselenenyl chloride and silver trifluoromethanesulfonate.It performs selenium-induced cyclization of β,γ-, γ,δ-, and δ,ε-unsaturated carboxylic acids.
- Murata, Shizuaki,Suzuki, Toshiyasu
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p. 849 - 852
(2007/10/02)
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- ORGANOSELENIUM-INDUCED CYCLIZATIONS IN ORGANIC SYNTHESIS
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A number of organoselenium reagents are introduced as efficient initiators of ring closures leading from unsaturated substrates to lactones, cyclic ethers, cyclic thioethers, N-heterocycles and carbocycles.These cyclizations often proceed with high ring selectivity and stereoselectivity and are accompained by the incorporation of the phenylseleno group (PheSe) into the final product.Methods are described for the effective removal of this group (PheSe) by oxidation or reduction achieving unsaturation or saturation.Finally the successful application of this Se-based methodology to the synthesis of stable and biologically active prostacyclins is outlined.Representative experimental procedures are included.
- Nicolaou, K.C.
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p. 4097 - 4109
(2007/10/02)
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- Cyclofunctionalisation of unsaturated acids with benzeneselenenyl chloride. Kinetic and thermodynamic aspects of the rules for ring closure
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Experimental procedures are described for the synthetically useful reaction by which olefinic acids are converted into lactones carrying a benzeneseleno-group. Data are presented to define some of the mechanistic details of this type of cyclofunctionalisation and kinetic and thermodynamic factors relevant to the Rules for Ring Closure are discussed. A nomenclature is introduced for a treatment of ring-fusion stereochemistry.
- Clive, Derrick L.J.,Russell, Charles G.,Chittattu, Gim,Singh, Alok
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p. 1399 - 1408
(2007/10/02)
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