- Kinetic Study for Reactions of Phenylseleno Radical with Vinyl Monomers
-
The reactivities of the phenylseleno radical (PheSe.) generated by flash photolysis of diphenyl diselenide have been determined.Low reactivities of PhSe. toward oxygen, hydrogen -atom donors, and halogen-atom donors have been confirmed.With vinyl monomers (CH2=CHY) PhSe. reacts in a reversible fashion; by the addition of oxygen as a selective radical trap to the adduct radicals (PhSeCH2C.HY), the absolute addition rate constants have been determined.The reverse rate constants and the equilibrium constants have been estimated as relative ones from which the thermodynamic stabilities of the adduct radicals have been elucidated.The addition rates increase mainly with the stabilities of the adduct radicals and subsequently with the polar nature of the transition state.The lower reactivity of PhSe. compared with the phenylthio radical (PhS.) is attributed to the greater stabilization of an unpaired electron in PhSe. than that in PhS..
- Ito, Osamu
-
-
Read Online
- Trifluoromethylthiolative 1,2-difunctionalization of alkenes with diselenides and AgSCF3
-
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
-
-
Read Online
- Laser-flash photolysis of naphthyl diselenides; Reactivities of naphthylseleno radicals
-
Transient absorption spectra of 1-naphthylseleno (1-NaphSe·), and 2-naphthylseleno (2-NaphSe·) radicals, which are generated by laser-flash photolysis of the corresponding diselenides, were observed. The reactions of 1-NaphSe·, and 2-NaphSe· with 2-methyl-1,3-butadiene and α-methylstyrene were investigated by following the decay rates of these seleno radicals. By both steady-state and laser-flash photolysis, it is proved that these seleno radicals add to alkenes in a reversible manner. The reaction rate constants for such reversible addition reactions were determined by conducting the reaction in the presence of O2, which traps selectively the carbon-centered radicals formed by the addition reaction of the seleno radicals to the alkenes. The reactivity of 2-NaphSe· is higher than that of 1-NaphSe·, both of which are less reactive than PhSe·. These reactivities were interpreted with the properties of SOMO calculated by MO method.
- Alam,Ito,Koga,Quchi
-
-
Read Online
- Efficient Syntheses of Diselenides from Selenols
-
Diselenides are quite instantaneously and quantitatively prepared by oxidation of selenols with 30 percent aqueous hydrogen peroxide or with the corresponding seleninic acids.
- Krief, A.,Mahieu, A. F. De,Dumont, W.,Trabelsi, M.
-
-
Read Online
- Stereoselective synthesis of (E)-vinylic selenides by palladium catalyzed cross-coupling reactions
-
Hydrozirconation of arylselenoethynes gives zirconium (IV) complexes 3, which are cross-coupled with aryl halides in the presence of tetrakis (triphenylphosphine) palladium catalyst to afford (E)-vinylic selenides 5 in high yield.
- Huang, Xian,Zhu, Liu-Sheng
-
-
Read Online
- A CONVENIENT SYNTHESIS OF PHENYL SELENOCYANATE
-
Treatment of benzeneselenenyl chloride with trimethylsilyl cyanide in various organic solvents provided phenyl selenocyanate in virtually quantitative yield.The reaction presents a very simple preparation of the useful selenenylation agent.
- Tomoda, Shuji,Takeuchi, Yoshito,Nomura, Yujiro
-
-
Read Online
- One-pot synthesis of 1-(E)-phenylethenyl-1,2,3-triazoles by sequential click-elimination reaction from 2-azido-1-phenyl-1-(Phenylseleno)ethane
-
A new convenient one-pot, two-step procedure involving sequential click chemistry and oxidation-elimination reaction for the preparation of 1,4-disubstituted 1,2,3-triazoles bearing 1-(E)-phenylethenyl group from 2-azido-1-phenyl-1-(phenylseleno)ethane is described. The prominent features of this protocol are mild reaction conditions, operational simplicity, and good to high yields of products, as well as avoidance of the isolation of the selenated intermediate. Supplementary materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements for the following free supplemental files: Additional figures.
- Su, Hai-You,Sheng, Shou-Ri,Zhang, Xiao-Lan,Ding, Xiao-Ying,Cai, Ming-Zhong
-
-
Read Online
- CuO nanoparticles-catalyzed a novel method to the synthesis of symmetrical diselenides from aryl halides: selenoamide as an organic Se-donor reagent
-
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
-
-
Read Online
- Allylic and Propargylic Phenyl Selenide Oxygenation by Cyclohexanone Oxygenase: -Sigmatropic Rearrangement of the Enzyme-generated Selenoxide
-
Enzymic oxidation of propargylic and allylic selenides has been carried out and the resulting selenoxides found to readily undergo 2,3-sigmatropic rearrangement; the propargylic product undergoes fragmentation while the allylic product yields racemic alcohols.
- Latham, John A.,Branchaud, Bruce P.,Chen, Y.-C. Jack,Walsh, Christopher
-
-
Read Online
- Chemoselective reduction of organoselenocyanates to diselenides and selenolates
-
Selenocyanates produce selenolates or diselenides on reaction with metal hydrides (NaH, LiHBEt3, LiBH4, NaBH4). The former transformation is performed with 2 molar equivalents of sodium hydride or lithium triethyl borohydride or 1.25 molar equivalent of metal borohydrides. The second one is performed with lower amount of reducing agent (1 molar equivalent of sodium hydride or lithium triethyl borohydride or 0.25 equivalent of metal borohydrides). Intermediate formation of a selenol or a selenolate which reacts on the unreacted selenocyanate is suspected in the later transformation.
- Krief, Alain,Delmotte, Cathy,Dumont, Willy
-
-
Read Online
- TRANSITION METAL-PROMOTED REACTIONS.VI. PALLADIUM(II)-PROMOTED OXIDATIVE COUPLING OF ETHYL ACRYLATE AND RELATED TERMINAL OLEFINS IN THE PRESENCE OF BENZENESELENENYL BROMIDE
-
Treatment of ethyl acrylate and related terminal olefins with benzeneselenenyl bromide under the conditions of the Heck reaction yields oxidative coupling products incorporated with two phenylselenenyl groups.The mechanism for this reaction is briefly discussed.
- Luh, Tien-Yau,So, Wan Hung,Tam, S.W.
-
-
Read Online
- Samarium diiodide-induced reduction of amorphous selenium: A facile synthesis of diaryl diselenides
-
Samarium diiodide reduces amorphous selenium to Se2/2- in THF. Subsequent addition of aryldiazonium fluoborates affords diaryl diselenides in moderate to good yields.
- Zhang,Jia,Zhou
-
-
Read Online
- Thermal stability and reaction of chalcogen-containing metallocenic compounds with elemental chalcogens
-
Dissymmetrical four-membered bimetallocenacycles (t-BuC5H4)2M(μ-S)2M'-(RC5H4)2 (M, M' = Zr, Hf; R = H, t-Bu) have been prepared and found to give redistribution products in solution at 190 deg C; identification of these products shows that the reaction involves exclusive cleavage of a metal-sulfur bond.Elemental sulfur and selenium react with chalcogen-containing complexes.The reaction is shown to involve the introduction of chalcogenic species in place of the ?-ligands of the complex to give either four-membered bimetallic complexes or catenated pentachalcogen metallocenic compounds.Some examples of insertion of sulfur and tellurium into the zirconium-methyl bond are also described.
- Tainturier, Gerard,Fahim, Mohammed,Trouve-Bellan, Gwenaaelle,Gautheron, Bernard
-
-
Read Online
- Selenium halide-induced bridge formation in [2.2]paracyclophanes
-
An addition/elimination sequence of selenium halides to pseudo-geminally bis(acetylene) substituted [2.2]paracyclophanes leads to new bridges with an endo -exo-diene substructure. The reactions have been found to be sensitive to the substitution of the ethynyl group. The formation of dienes with a zig-zag configuration is related to that observed for non-conjugated cyclic diynes of medium ring size.
- Sarbu, Laura G.,Hopf, Henning,Jones, Peter G.,Birsa, Lucian M.
-
-
Read Online
- Intramolecular oxyselenenylation and deselenenylation reactions in water, conducted by employing polymer-supported arylselenenyl bromide
-
After immobilizing arylselenenyl bromide on polymer resin, the oxyselenenylation reaction of olefin was carried out in water. An amphiphilic polymer-supported arylselenenyl bromide was employed, and various intramolecular oxyselenenylation and deselenenylation reactions proceeded smoothly in water in fair chemical yields (up to an 83% yield).
- Fujita, Ken-Ichi,Hashimoto, Shigeru,Oishi, Akihiro,Taguchi, Yoichi
-
-
Read Online
- Metathesis of N-Silyl Compounds with Selenenyl Chlorides. First Preparation of a Selenenyl Azide and a Triselenenamide
-
The reaction of trimethylsilyl azide with mesityleneselenenyl chloride afforded mesityleneselenenyl azide, and tris(trimethylsilyl)amine reacted with benzeneselenenyl chloride to produce tribenzeneselenenamide.
- Back, Thomas G.,Kerr, Russell G.
-
-
Read Online
- Electrochemical investigation of the chloroselenobenzene under its atmosphere-sensitive characteristics
-
Electrochemical oxidation and reduction of the chloroselenobenzene were described in a catalyst-less and mild solution through cyclic voltammetry and controlled-potential electrolysis under air and nitrogen atmosphere. By electrogenerated intermediates and controlling conditions, unique compounds, including a Diselenol, Diselenide, and Polyselenid, were synthesized in good to excellent yields and purities. These compounds can be oxidized at the surface of the carbon electrode to produce reactive precursors with several Michael addition positions for further investigations.
- Chegini, Parisa,Khakyzadeh, Vahid,Varmaghani, Fahimeh
-
-
Read Online
- A convenient new method for the preparation of diaryl diselenide
-
Diaryliodonium salts react with sodium O, O-diethyl phosphoroselenoate in ethano-DMF at 70-80°C then hydrolyzed in basic medium and oxidized at room temperature to afford symmetric diaryl diselenides in better yields.
- Liu,Chen
-
-
Read Online
- Perhydroazulenes. 7. Effect of a tert-Butyl Substituent at C-6 upon the Properties of the 4-Keto Derivatives
-
The four diastereoisomeric 6-tert-butyl-4-ketoperhydroazulenes 4,6,8, and 10 have been prepared.The previously unknown cis-syn isomer 6 was characterized with spectra, an analysis, and a crystal structure of its oxime.The two stereoisomeric enol acetates 11 and 12 were prepared and each isomer was used to generate the corresponding lithium enolate 13 or 16.In each case methylation of one of these enolates formed a monoalkylated product containing more than 90percent of the cis-fused isomer 14 or 17.The alkylated products were characterized by spectra, analyses, and crystal structures.The probable conformations for the enolates and the alkylated products are discussed.
- House, Herbert O.,Nomura, Glenn S.,VanDerveer, Don
-
-
Read Online
- Catalyst-free gem-difunctionalization of fluoroalkyl-substituted diazo compound with diselenide or disulfide and NFSI
-
The gem-difunctionalization of fluoroalkyl-substituted diazo compounds by utilizing diselenides or disulfides and NFSI under catalyst-free and mild conditions is reported. A series of gem-aminoselenolation and gem-aminosulfonylation products bearing fluoroalkyl substituents were obtained in high to excellent yields. Different types of conjugated diazo compounds are also applicable to this transformation. Preliminary mechanistic studies indicate that a selenoimidate intermediate generated from diselenide and NFSI is involved for this transformation.
- Li, Jiuling,Ma, Chaoqun,Xing, Dong,Hu, Wenhao
-
-
Read Online
- The Anodic Acetoxylation of Alkylarylselenides
-
Electrooxidation of alkylarylselenides in methanol in the presence of sodium acetate leads to the acetoxylation of the methylene group of selenides
- Jouikov, Viatcheslav,Ivkov, Valery,Fattahova, Dina
-
-
Read Online
- Preparation of α,α-Bis(phenylseleno)ketones
-
α,α-Bis(phenylseleno)ketones have been synthesized by phenylselenenylation of enolates derived from α-phenylseleno ketones.Depending on the structure of the ketones, three experimental procedures were adopted.
- Ponthieux, Sylvain,Outurquin, Francis,Paulmier, Claude
-
-
Read Online
- Chalcogen-rich lanthanide clusters: Cluster reactivity and the influence of ancillary ligands on structure
-
Ytterbium metal reacts with PhEEPh (E = S, Se, Te) and elemental Se in pyridine to give (pyridine)8Yb4(SeSe)2(Se)2(μ 2-SPh)2(SPh)2, (py)8Yb4Se(SeSe)3(SeSeSePh)(Se 0.38SePh), and (py)8Yb4Se(SeSe)3-(SeSeTePh)(SeTePh), respectively. The SePh and TePh compounds contain a square array of Ln(III) ions all connected to a central Se2- ligand. Three edges of the square are bridged by diselenide ligands, with the fourth SeSe unit coordinating to an EPh ligand that has been displaced from an inner Yb coordination sphere. Differences in the two compounds have their origin in the relative strength of the Yb - E(Ph) bond. In the TePh compound, there is a complete insertion of Se into the remaining Yb - Te(Ph) bond to give a terminal SeTePh ligand, while in the SePh compound there is a compositional disorder in the structure comprised of a terminal SePh ligand and a minor component that has Se inserted into the Yb - Se(Ph) bond to give a terminal SeSePh ligand. The thiolate compound differs dramatically, crystallizing as a rhombohedral array of four Yb(III) ions connected by a pair of μ3-Se2- ligands, with the edges of the rhombus spanned by alternating diselenide and SPh. The SPh coordinate directly to Yb(III) ions in terminal or bridging modes. Cluster interconversion is facile: (py)4Yb(SePh)2 reduces (py)8Yb4Se(SeSe)3(SeSeSePh)(Se 0.38SePh) to give the cubane cluster [(py)2YbSe(SePh)]4, and the cubane reacts with elemental Se to give (py)8Yb4Se(SeSe)3(SeSeSePh)-(Se 0.38SePh). Upon thermolysis, these compounds give YbSex.
- Kornienko,Emge,Brennan
-
-
Read Online
- Dihydroxy phenylselenonium p-toluenesulfonate; preparation and use in the recycling of selenium reagents
-
Dihydroxy phenylselenonium p-toluenesulfonate is prepared by oxidation of diphenyl diselenide with hydrogen peroxide in the presence of p-toluenesulfonic acid. The process which is carried out as a titration has been applied as the key step in a preparation of very pure diphenyl diselenide and in the recycling of benzeneseleninic acid.
- Henriksen, Lars,Stuhr-Hansen, Nicolai
-
-
Read Online
- In situ synthesis of CuO nanoparticles over functionalized mesoporous silica and their application in catalytic syntheses of symmetrical diselenides
-
A versatile and novel catalyst, CuO nanoparticles immobilized over functionalized mesoporous silica (nCuO-FMS), has been synthesized over an organically modified mesoporous silica framework following a facile synthetic route. The surface of the silica support (SBA-15) is first grafted with the 3-aminopropyl silane group and then further functionalized with tris(4-formylphenyl)amine. The reaction is performed in such a way that a few -CHO groups remain free for further functionalization. Finally, the CuO nanoparticles immobilized on mesoporous silica are obtained by a one pot reaction between the functionalized silica, 2-aminophenol and CuCl2. The product obtained has been used as a catalyst for the syntheses of symmetrical diselenides in the presence of KOH as the base and dimethyl sulphoxide (DMSO) as the solvent. The materials have been characterized thoroughly by X-ray powder diffraction, nitrogen adsorption-desorption studies, transmission electron microscopy, thermal analysis and different spectroscopic techniques. The Cu content of the sample has been determined by atomic absorption spectrophotometry (AAS). The products of the catalytic studies have been identified and estimated by NMR spectroscopy. Almost 78% isolated yield could be achieved at 363 K within 3 hours of the reaction and the catalyst, nCuO-FMS, can be recycled at least up to five catalytic cycles.
- Das, Trisha,Chatterjee, Rana,Majee, Adinath,Uyama, Hiroshi,Morgan, David,Nandi, Mahasweta
-
-
Read Online
- Se,Se′-diphenyl carbonodiselenoate: Preparation and characterization of its molecular structure and thermal reactivity
-
Reaction of dipotassium nitroacetate with benzeneselenenyl bromide produces the title compound as a thermally unstable product, which has been characterized by X-ray crystallography.
- Lowe,Chandrasekaran,Day,Rosen
-
-
Read Online
- Chemoselective reduction of organoselenocyanates to diselenides
-
Selenocyanates possess an extremely high propensity to produce diselenides on reaction with selenols or selenolates. This is effectively observed when one molar equivalent of metal hydride or lithium triethyl borohydride or one fourth molar equivalent of metal borohydrides are reacted with organic selenocyanates.
- Krief, Alain,Delmotte, Cathy,Dumont, Willy
-
-
Read Online
- Iodine mediated synthesis of diaryl diselenides using SeO2 as a selenium source
-
A simple, eco-friendly and convenient procedure has been developed for the synthesis of diphenyl diselinides from readily available aryl boronic acids by reaction with SeO2 in the presence of iodine under simple conditions. The methodology is reported about 19 examples and applicable to a broad scope of aryl boronic acids containing electron-rich and electron-poor substituents. Apart from being milder and environmentally benign conditions, this synthetic protocol comprises a novel, reliable methodology to give good to high yields of the desired diaryl diselenides.
- Kommula, Dileep,Li, Qing,Ning, Siyang,Liu, Wujun,Wang, Qian,Zhao, Zongbao K.
-
-
Read Online
- Visible Light-Induced Cascade Cyclization of 3-Aminoindazoles, Ynals, and Chalcogens: Access to Chalcogen-Containing Pyrimido[1,2- b]-indazoles
-
A direct cascade cyclization of 3-aminoindazoles, ynals, and accessible chalcogens facilitated by visible light has been developed. A series of fluoroactive selenium/tellurium-substituted pyrimido[1,2-b]-indazoles were easily accessed in moderate to good yields with a broad scope. Furthermore, we surveyed the spectral properties of selenide pyrimido[1,2-b]-indazoles prepared by this method.
- Zhou, Jinlei,Li, Wen,Zheng, Huitao,Pei, Yongyan,Liu, Xiang,Cao, Hua
-
supporting information
p. 2754 - 2759
(2021/04/12)
-
- Green preparation method of aryl diselenium ether type organic selenium compound
-
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.
- -
-
Paragraph 0104-0116
(2021/11/14)
-
- Copper-catalyzed three-component ortho-selective selenation of phenols
-
An efficient and convenient copper-catalyzed three-component reaction has been developed for the arylselenation of phenols with Se powder and aryl iodides. This one-pot procedure provides a straightforward approach to the synthesis of ortho-arylselenylphenols with high regioselectivity. This practical process shows good functional group tolerance, providing the corresponding products in moderate to good yields.
- Luo, Run,Guo, Lina,Su, Meiyun,Liu, Wenjie,Wang, Shaohua
-
p. 896 - 901
(2021/07/19)
-
- Blue light-promoted radical sulfoximido-chalcogenization of aliphatic and aromatic alkenes
-
A transition metal-free synthesis ofN-(arylthio/seleno)ethyl sulfoxidminesviablue light-promoted radical sulfoximido-chalcogenization of aliphatic and aromatic alkenes was developed. The sulfoximidation process demonstrated high chemoselectivity and allowed a broad substrate scope, completing the sulfoximido-chalcogenization of alkenes in good yields.
- Chen, Hongyi,Chen, Li,He, Ze,Zeng, Qingle
-
supporting information
p. 2624 - 2627
(2021/04/21)
-
- Highly selective radical isothiocyano-chalcogenization of alkenes with NH4SCN in water
-
In the presence of catalytic amounts of molecular iodine and stoichiometric potassium persulfate, a green, highly chemoselective, regioselective and cis-selective radical isothiocyano-chalcogenization of alkenes with NH4SCN in water is disclosed. This three component reaction features high selectivities, an environmentally benign process, mild conditions, high yields, excellent functional-group tolerance, and broad substrate scope. The resulting products can be further transformed into other molecules with structural similarities of these compounds to bioactive analogs.
- He, Ze,Kang, Xiaokang,Xu, Chao,Zeng, Qingle
-
supporting information
p. 7544 - 7548
(2021/10/12)
-
- Preparation of selenofunctionalized heterocycles via iodosobenzene-mediated intramolecular selenocyclizations of olefins with diselenides
-
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
-
supporting information
p. 2587 - 2591
(2021/03/15)
-
- Metal-free synthesis of unsymmetrical selenides from pyridinium salts and diselenides catalysed by visible light
-
We report the first metal-free selenolations of pyridinium salts with diselenides to prepare unsymmetrical organoselenides catalysed by visible light. This protocol is an efficient and green method for the preparation of unsymmetrical organoselenides because metal-free conditions and readily accessible diselenides are used.
- Ji, Liangshuo,Qiao, Jiamin,Li, Ankun,Jiang, Zeyi,Lu, Kui,Zhao, Xia
-
supporting information
(2021/05/04)
-
- FeCl3-catalyzed three-component aryl-selenylation of alkenes
-
FeCl3-catalyzed three-component aryl-selenylation of alkenes with good to excellent yields has been disclosed. This method is characterized by synthesis of complicated products in a single-step reaction, simple operation and readily available commercially reagents. Finally, a reasonable mechanism of FeCl3-catalyzed aryl-selenylation is proposed.
- Xu, Chao,He, Ze,Yang, Hongqin,Chen, Hongyi,Zeng, Qingle
-
-
- Visible-light-driven radical 1,3-addition of selenosulfonates to vinyldiazo compounds
-
Herein, we report a visible-light-driven radical 1,3-selenosulfonylation of vinyldiazo compounds with selenosulfonates, providing various γ-seleno allylic sulfones in good yields. This photochemical reaction was carried out at room temperature in an open flask using ethyl acetate as the solvent without any photocatalysts or additives. The control experiments corroborated that the 1,3-addition proceeded via a radical-chain propagation process. The synthetic applications of the resulting products were demonstrated by deselenization, reduction, bromination and allylation.
- Li, Weiyu,Zhou, Lei
-
supporting information
p. 6652 - 6658
(2021/09/10)
-
- Palladium-Catalyzed Carbonylative Synthesis of Aryl Selenoesters Using Formic Acid as an Ex Situ CO Source
-
A new catalytic protocol for the synthesis of selenoesters from aryl iodides and diaryl diselenides has been developed, where formic acid was employed as an efficient, low-cost, and safe substitute for toxic and gaseous CO. This protocol presents a high functional group tolerance, providing access to a large family of selenoesters in high yields (up to 97%) while operating under mild reaction conditions, and avoids the use of selenol which is difficult to manipulate, easily oxidizes, and has a bad odor. Additionally, this method can be efficiently extended to the synthesis of thioesters with moderate-to-excellent yields, by employing for the first time diorganyl disulfides as precursors.
- Alves, Diego,Sacramento, Manoela Do,Santi, Claudio,Schwab, Ricardo S.,Teixeira, Wystan K. O.,Yano De Albuquerque, Danilo
-
supporting information
(2022/01/12)
-
- Visible-light-induced oxidative coupling of vinylarenes with diselenides leading to α-aryl and α-alkyl selenomethyl ketones
-
A visible-light-induced oxidative coupling of diselenides with readily available vinylarenes is demonstrated. This benign protocol allows one to access a wide range of α-aryl and α-alkyl selenomethyl ketones in good yields with excellent functional group compatibility. The distinct advantages of this protocol over all previous methods include the use of a green solvent and air as an oxidant and the lack of a photocatalyst, a base, and an oxidant as well as better green chemistry matrices. Furthermore, the title reaction can be performed with natural sunlight, the most sustainable energy source imaginable. Additionally, the mild reaction conditions, easy operation and suitability for the modification of styrene-functionalized biomolecules make the current reaction system a more attractive method for the synthesis of a variety of medicinal and agrochemical compounds of interest.
- Liu, Gong-Qing,Yi, Wei,Wang, Peng-Fei,Liu, Ji,Ma, Meng,Hao, Da-Yun,Ming, Liang,Ling, Yong
-
supporting information
p. 1840 - 1846
(2021/03/09)
-
- Diphenyl Diselenide-Catalyzed Synthesis of Triaryl Phosphites and Triaryl Phosphates from White Phosphorus
-
Industrially important triaryl phosphites, traditionally prepared from PCl3, have been synthesized by a diphenyl diselenide-catalyzed one-step procedure involving white phosphorus and phenols, which provides a halogen- and transition metal-free way to these compounds. Subsequent oxidation of triaryl phosphites produces triaryl phosphates and triaryl thiophosphates. Phosphorotrithioates are also prepared efficiently from aromatic thiols and aliphatic thiols.
- Zhang, Yue,Cai, Ziman,Chi, Yangyang,Zeng, Xiangzhe,Chen, Shuanghui,Liu, Yan,Tang, Guo,Zhao, Yufen
-
supporting information
p. 5158 - 5163
(2021/07/20)
-
- Synthesis of Seleno Oxindoles via Electrochemical Cyclization of N-arylacrylamides with Diorganyl Diselenides
-
The tandem cyclization of acrylamide with diselenides facilitated by electrochemical oxidation was successfully developed. This strategy provided an environmentally friendly method for the construction of C?Se bond. A series of seleno oxindoles with pharmacological activity were obtained by using this well-designed tandem cyclization strategy. The in vitro antitumor activity of the compounds was also screened through MTT assay. Results showed that the seleno oxindoles exhibited better antitumor activity than other oxindole derivatives. (Figure presented.).
- Wang, Xin-Yu,Zhong, Yuan-Fang,Mo, Zu-Yu,Wu, Shi-Hong,Xu, Yan-Li,Tang, Hai-Tao,Pan, Ying-Ming
-
supporting information
p. 208 - 214
(2020/12/04)
-
- Click Reaction of Selenols with Isocyanates: Rapid Access to Selenocarbamates as Peroxide-Switchable Reservoir of Thiol-Peroxidase-Like Catalysts
-
Selenols react with isocyanates under mild catalyst-free conditions to generate selenocarbamates in good yield and with high selectivity over potentially competing nucleophilic additions. The methodology enables the incorporation of a wide variety of functional groups providing access to a broad array of densely functionalised selenocarbamates. In the presence of competing heteroatom-centered nucleophiles, isocyanates selectively couple with selenols. Selenocarbamates exhibited thiol-peroxidase-like properties, enabling the reduction of hydrogen peroxide at the expense of thiols, which are converted into the corresponding disulfides. A series of control experiments suggested that the catalytic mechanism proceeds through a pathway, involving a H2O2-promoted transcarbamoylation reaction leading to a thiocarbamate with concomitant releasing of catalytically active selenolate anions. By undergoing peroxide-driven thiol-selenol exchange, selenocarbamates behave as equivalents of selenolate anions with thiol-peroxidase-like activity. (Figure presented.).
- Capperucci, Antonella,Petrucci, Alessandra,Faggi, Cristina,Tanini, Damiano
-
p. 4256 - 4263
(2021/07/17)
-
- Lead optimization generates selenium-containing miconazole CYP51 inhibitors with improved pharmacological profile for the treatment of fungal infections
-
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
-
-
- Visible Light-Promoted Selenylation/Cyclization of Enaminones toward the Formation of 3-Selanyl-4H-Chromen-4-Ones
-
A simple and efficient visible-light-promoted selenylation/cyclization of enaminones have been realized for the practical synthesis of 3-selanyl-4H-chromen-4-ones. This reaction is performed in the mild conditions, no transition metal catalyst or photocatalysts and no additional oxidants are required. In addition, the 3-selanyl-4H-chromen-4-ones could be easily converted to selanyl-functionalized pyrimidines by reacting with benzamidine substrates. (Figure presented.).
- Liu, Hao-Yang,Zhang, Jia-Rong,Huang, Guo-Bao,Zhou, Yi-Huan,Chen, Yan-Yan,Xu, Yan-Li
-
supporting information
p. 1656 - 1661
(2021/02/12)
-
- Nickel-Catalyzed Intramolecular Decarbonylative Coupling of Aryl Selenol Esters
-
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
-
supporting information
p. 2084 - 2088
(2021/03/01)
-
- Synthesis method of selenium-containing isochroman compound
-
The invention discloses a synthesis method of a selenium-containing isochroman compound. The synthesis method comprises the following steps: under the protection of nitrogen, adding N-phenylseleno saccharin (NPSSac) into a reactor, then adding dichloromethane to completely dissolve the N-phenylseleno saccharin, adding a 1-[(cinnamoxy) methyl]-3, 4, 5-trimethoxy benzene compound and boron trifluoride diethyl etherate after the N-phenylseleno saccharin is completely dissolved, stirring at 20-60 DEG C for 2-6 hours until the reaction is complete, and after the reaction is finished, quenching, extracting, combining organic phases, drying, concentrating, separating and purifying to obtain the selenium-containing isochroman compound. The synthesis method disclosed by the invention is relatively easy to operate, mild in reaction condition, relatively high in yield, environment-friendly and suitable for large-scale industrial production.
- -
-
Paragraph 0046; 0055-0056
(2021/05/29)
-
- Synthesis method of 2-benzoxepin compound
-
The invention discloses a synthesis method of a 2-benzoxepin compound. The method comprises the following specific steps: under the protection of nitrogen, adding N-phenylseleno-phthalimide into a reactor, then adding anhydrous dichloromethane to dissolve the N-phenylseleno-phthalimide, then adding a 1-[(cinnamyl) methyl]-3, 4, 5-trimethoxybenzene compound, taking zinc chloride as a catalyst, reacting at room temperature, adding saturated sodium bicarbonate for quenching after the reaction is finished, extracting by dichloromethane, combining organic phases, drying by anhydrous magnesium sulfate, concentrating under reduced pressure, and performing silica gel rapid chromatographic purification by thin-layer chromatography silica gel to obtain the 2-benzoxepin compound. The method is simple in reaction operation, mild in reaction condition, relatively high in yield, environment-friendly and suitable for large-scale industrialized production.
- -
-
Paragraph 0045; 0053; 0057; 0065
(2021/05/29)
-
- Synthesis method of isochroman compound
-
The invention discloses a synthesis method of an isochroman compound, which comprises the following steps of adding dichloromethane and phosphorus tribromide into 3, 4, 5-trimethoxy benzyl alcohol, and reacting to obtain 1-bromomethyl-3, 4, 5-trimethoxy benzene, adding tetrahydrofuran, cinnamyl alcohol, sodium hydride and 1-bromomethyl-3, 4, 5-trimethoxybenzene into a reactor, and reacting to obtain 1-[(cinnamyl oxy)methyl]-3, 4, 5-trimethoxybenzene, adding cyanuric acid into a reactor containing a potassium hydroxide aqueous solution to react, dropwise adding a silver nitrate aqueous solution, and reacting to obtain silver isocyanurate, adding silver isocyanurate, phenyl selenium bromide and anhydrous dichloromethane into a reactor, and reacting to obtain N, N, N-triphenyl seleno isocyanurate, reacting N, N, N-triphenyl seleno isocyanurate, dichloromethane, boron trifluoride diethyl etherate and a 1-[(cinnamyl oxy)methyl]-3, 4, 5-trimethoxybenzene compound to obtain a target product. The method is simple in reaction operation, mild in reaction condition, relatively high in yield and environment-friendly.
- -
-
Paragraph 0046; 0054; 0060-0068; 0073; 0081
(2021/05/15)
-
- Clarification on the reactivity of diaryl diselenides toward hexacyclohexyldilead under light
-
In this study, the reactivity of organochalcogen compounds toward a representative alkyl-lead bond compound under light was investigated in detail. Under light irradiation, the Cy-Pb bond of Cy6 Pb2 (Cy = cyclohexyl) undergoes homolytic cleavage to generate a cyclohexyl radical (Cy?). This radical can be successfully captured by diphenyl diselenide, which exhibits excellent carbon-radical-capturing ability. In the case of (PhS)2 and (PhTe)2, the yields of the corresponding cyclohexyl sulfides and tellurides were lower than that of (PhSe)2. This probably occurred due to the low carbon-radical-capturing ability of (PhS)2 and the high photosensitivity of the cyclohexyl-tellurium bond.
- Hung, Vu Thai,Kodama, Shintaro,Nomoto, Akihiro,Ogawa, Akiya,Tran, Cong Chi,Yamamoto, Yuki
-
-
- A greener protocol for the synthesis of phosphorochalcogenoates: Antioxidant and free radical scavenging activities
-
In this contribution, a metal- and base-free protocol has been developed for the synthesis of phosphorochalcogenoates (Se and Te) by using DMSO as solvent at 50 °C. A variety of phosphorochalcogenoates were prepared from diorganyl dichalcogenides and H-phosphonates, leading to the formation of a Chal-P(O) bond, in a rapid procedure with good to excellent yields. A full structural elucidation of products was accessed by 1D and 2D NMR, IR, CGMS, and HRMS analyses, and a stability evaluation of the phosphorochalcogenoates was performed for an effective operational description of this simple and feasible method. Typical 77Se{1H} (δSe = 866.0 ppm), 125Te{1H} (δTe = 422.0 ppm) and 31P{1H} (δP = ?1.0, ?13.0 and ?15.0 ppm) NMR chemical shifts were imperative to confirm the byproducts, in which this stability study was also important to select some products for pharmacological screening. The phosphorochalcogenoates were screened in vitro and ex vivo tests for the antioxidant potential and free radical scavenging activity, as well as to investigation toxicity in mice through of the plasma levels of markers of renal and hepatic damage. The pharmacological screening of phosphorochalcogenoates indicated that compounds have antioxidant propriety in different assays and not changes plasma levels of markers of renal and hepatic damage, with excision of 3g compound that increased plasma creatinine levels and decreased plasma urea levels when compared to control group in the blood mice. Thus, these compounds can be promising synthetic antioxidants that provide protection against oxidative diseases.
- Mailahn, Daniela H.,Iarocz, Lucas E.B.,Nobre, Patrick C.,Perin, Gelson,Sinott, Airton,Pesarico, Ana Paula,Birmann, Paloma T.,Savegnago, Lucielli,Silva, Márcio S.
-
-
- Synthesis of β-hydroxy aryl selenides via transition-metal-free three-component reaction of arylamines, elemental selenium, and epoxides
-
An efficient protocol for the construction of valuable β-hydroxy aryl selenides from easily available arylamines, elemental selenium, and epoxides through a transition-metal-free radical process is described. A wide variety of β-hydroxy aryl selenides were obtained in good to excellent yields with excellent stereo- and regioselectivity. In this reaction, two C-Se bonds can be built along with the cleavage of a C-N and C-O bond, demonstrating the high step economy and efficiency of this approach.
- Wang, Hongwei,Li, Hongchen,Bai, Yalong,Hei, Yanling,Chen, Junwei,Yu, Guoqi,Zhou, Yun-Bing
-
p. 3621 - 3629
(2021/06/21)
-
- Metal-Free Synthesis of Unsymmetrical Aryl Selenides and Tellurides via Visible Light-Driven Activation of Arylazo Sulfones
-
A protocol for the visible light driven preparation of unsymmetrical (hetero)aryl selenides and tellurides is described herein. The method exploits the peculiar photoreactivity of arylazo sulfones that act as thermally stable, precursors of aryl radicals under both photocatalyst- and additive-free conditions. The method developed shows an impressive versatility (more than fifty compounds isolated).
- Fagnoni, Maurizio,Li, Ankun,Li, Yuxuan,Liu, Junjie,Lu, Kui,Protti, Stefano,Shan, Xiwen,Tian, Miaomiao,Zhao, Xia
-
p. 7358 - 7367
(2020/12/01)
-
- Lysosomal Reacidification Ameliorates Vinyl Carbamate-Induced Toxicity and Disruption on Lysosomal pH
-
Ethyl carbamate (EC) is a carcinogen toxicant, commonly found in fermented foods and beverages. The carcinogenic and toxic possibility of EC is thought to be related to its metabolite vinyl carbamate (VC). However, we found interesting mechanisms underlying VC-induced toxicity in this study, which were greatly different from EC. We first conducted a simple synthesis procedure for VC and found that VC possessed higher toxicity but failed to regulate levels of reactive oxygen species, glutathione, and autophagy. Notably, VC treatment resulted in upregulation of lysosomal pH, which was responsible for its cytotoxicity. Cyclic adenosine monophosphate (cAMP) pretreatment could enhance restoration of lysosomal acidity and ameliorate VC-induced damage. Inhibition of protein kinase A and cystic fibrosis transmembrane conductance regulator can block cAMP-induced cytoprotection. Together, our results provided the evidence for novel mechanisms of toxicity and possible protection method under VC exposure, which might give new perspectives on the study of EC-induced toxicity.
- Chen, Wei,Cui, Sunliang,Hu, Dongwen,Li, Yuting,Qi, Jifeng
-
p. 8951 - 8961
(2020/09/16)
-
- An efficient and practical method for the selective synthesis of sodium diselenide and diorganyl diselenides through selenium reduction
-
Studies on an efficient and practical method for the selective synthesis of diorganyl diselenides over diorganyl selenides are presented. Considering the discrepancies between reports on organoselenium compounds, we wanted to establish a tolerable synthetic method for diorganyl diselenides and investigate their characteristics. We optimized reaction conditions for sodium diselenide preparation using selenium, NH2NH2·H2O, and NaOH and, by treating the obtained sodium diselenide with various alkyl or aryl halides, achieved the selective synthesis of diorganyl diselenides in modest to good yields (57–88%) with good reproducibility. We further studied the mechanistic implication, the effects of solvent changes, and the stability of diorganyl diselenides.
- Lim, Yoo Jin,Shin, Na Hye,Kim, Chorong,Kim, Ye Eun,Cho, Hyunsung,Park, Myung-Sook,Lee, Sang Hyup
-
-
- Iron(III) chloride-promoted cyclization of α,-alkynic tosylhydrazones with diselenides: Synthesis of 4-(arylselanyl)-1: H-pyrazoles
-
A highly efficient iron(iii) chloride-promoted cyclization between α,-alkynic tosylhydrazones and diselenides to form a 4-(arylselanyl)-1H-pyrazole skeleton is studied. This reaction forms C-N and C-Se bonds in one step by utilizing inexpensive iron(iii) chloride instead of expensive transition metal additives. This strategy features easily synthesized substrates, mild reaction conditions and high tolerance to functional groups.
- Ji, Shun-Jun,Li, Fang-Hui,Li, Jian,Wang, Shun-Yi,Yao, Hai-Feng
-
supporting information
p. 1987 - 1993
(2020/03/23)
-
- Rhodium-Catalyzed Enantioselective Hydroselenation of Heterobicyclic Alkenes
-
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
-
supporting information
p. 2781 - 2785
(2020/03/30)
-
- Alkene: Versus alkyne reactivity in unactivated 1,6-enynes: Regio-And chemoselective radical cyclization with chalcogens under metal-And oxidant-free conditions
-
Herein, we have developed metal and oxidant-free visible light-promoted alkene vs. alkyne regio-And chemoselective radical cascade cyclization of electronically unbiased 1,6-enynes with chalcogens to synthesize substituted pyrrolidines bearing chalcogens. The reaction generated three new bonds, namely, C-SO2, C-C, and C-Se under extremely mild conditions. Furthermore, we achieved regio-And chemoselective mono-addition of aromatic thiophenols with unactivated 1,6-enynes. The key features of this protocol are broad substrate scope, environment-friendly conditions, operational simplicity, atom economy, and amenability to gram-scale synthesis. The mechanistic studies corroborate that the reaction proceeds via a radical pathway.
- Kudale, Vishal Suresh,Li, Jing,Mutra, Mohana Reddy,Tsai, Wu-Hsun,Wang, Jeh-Jeng
-
supporting information
p. 2288 - 2300
(2020/04/21)
-
- Continuous Electrochemical Synthesis of Iso-Coumarin Derivatives from o-(1-Alkynyl) Benzoates under Metal- and Oxidant-Free
-
A non-oxidant and metal-free strategy for synthesizing iso-coumarin by using a continuous electrochemical microreactor to initiate an oxidative cyclization reaction of o-(1-alkynyl) benzoate and radicals. This efficient and clean continuous electrosynthesis method not only avoids the complicated gas protection operation and production of by-products in the batch processes, but also help to overcome the difficulty that batch metal catalysis and electrocatalysis are difficult to scale up, and has the potential for pilot-scale experiment.
- Lin, Xinxin,Fang, Zheng,Zeng, Cuilian,Zhu, Chenlong,Pang, Xinyan,Liu, Chengkou,He, Wei,Duan, Jindian,Qin, Ning,Guo, Kai
-
supporting information
p. 13738 - 13742
(2020/10/02)
-
- Transition metal-free coupling reactions of benzylic trimethylammonium salts with di(hetero)aryl disulfides and diselenides
-
A new protocol was developed to synthesize (enantioenriched) thioethers and selenoethers from (chiral) benzylic trimethylammonium salts and di(hetero)aryl disulfides or diselenides. These syntheses were promoted by the presence of weak base and did not require the use of any transition metal, and resulted in the target products with good to excellent yields (72-94%). Using quaternary ammonium salts synthesized from enantiomerically enriched amines led to highly enantiopure benzylic thioethers and selenoethers (94-99% ee) with configurations reversed from those of their enantioenriched quaternary ammonium salts. This journal is
- Li, Fuhai,Wang, Dan,Chen, Hongyi,He, Ze,Zhou, Lihong,Zeng, Qingle
-
supporting information
p. 13029 - 13032
(2020/11/07)
-
- Visible-Light-Promoted Selenylative Spirocyclization of Indolyl-ynones toward the Formation of 3-Selenospiroindolenine Anticancer Agents
-
A metal-free and efficient visible-light-induced spirocyclization of indolyl-ynones with diselenides at room temperature under air atmosphere to prepare 3-selenospiroindolenines in moderate to good yields has been developed. The resulting products were tested for in vitro anticancer activity by MTT assay, and compounds 3 c and 3 e showed potent cancer cell-growth inhibition activities.
- Zhou, Xiu-Jie,Liu, Hao-Yang,Mo, Zu-Yu,Ma, Xian-Li,Chen, Yan-Yan,Tang, Hai-Tao,Pan, Ying-Ming,Xu, Yan-Li
-
supporting information
p. 1536 - 1539
(2020/04/20)
-
- Arylseleninic acid as a green, bench-stable selenylating agent: Synthesis of selanylanilines and 3-selanylindoles
-
Arylseleninic acids were used as an electrophilic selenium source in aromatic substitution reactions, using N,N-substituted anilines and indoles as nucleophiles at 70 °C for 6-15 h. A total of fourteen 4-selanylanilines and five 3-selanylindoles were selectively obtained in good to excellent yields. The starting benzeneseleninic acids are easily prepared from the respective diselenides, are bench stable and easy to handle, affording water as the only waste at the end of the reaction. This journal is
- Abenante, Laura,Anghinoni, Jo?o M.,Lenard?o, Eder J.,Padilha, Nathalia B.,Penteado, Filipe,Rosati, Ornelio,Santi, Claudio,Silva, Marcio S.
-
p. 5210 - 5217
(2020/07/23)
-
- Multistep Synthesis of Organic Selenides under Visible Light Irradiation: A Continuous-Flow Approach
-
The potential application of multistep continuous-flow systems has had a great impact on the syntheses of active pharmaceutical ingredients, natural products, and commodity chemicals. In this report, the highly efficient combination of a chemical reduction and a photochemical Csp2-H activation reaction for selenylation of biologically relevant electron-rich arenes was achieved by means of a continuous-flow process. First, the reduction of alkyl and aryl selenocyanates by Rongalite was achieved giving the corresponding diselenides; second, the photoactivation of the Se-Se bond resulted in the selenylation of electron-rich arenes, both steps from good to excellent yields. In all cases, the reaction time was shortened, and isolated yields were improved when compared to batch reaction conditions. Furthermore, connecting both reactions in a multistep continuous-flow sequence was possible even when reductive and photooxidative transformations were coupled.
- Heredia, Adrián A.,Soria-Castro, Silvia M.,Castro-Godoy, Willber D.,Lemir, Ignacio D.,López-Vidal, Martín,Bisogno, Fabricio R.,Argüello, Juan E.,Oksdath-Mansilla, Gabriela
-
supporting information
p. 540 - 545
(2020/03/26)
-
- O-(tert-butyl) Se-phenyl selenocarbonate: A convenient, bench-stable and metal-free precursor of benzeneselenol
-
A study by our laboratory shows that air, light and moisture stable O-(tert-butyl) Se-phenyl selenocarbonate could be employed as a safer, practical and efficient alternative to generate “in situ” benzeneselenol or benzeneselenolate anion under different and transition metal-free conditions. This procedure seems to be of general application since the nucleophilic selenium species obtained can be trapped by electrophiles such as alkyl halides, epoxides and electron-deficient alkenes and alkynes under different reaction conditions.
- Temperini, Andrea,Siciliano, Carlo
-
-
- Chemoselective and metal-free reduction of α,β-unsaturated ketones by: In situ produced benzeneselenol from O -(tert -butyl) Se-phenyl selenocarbonate
-
The carbon-carbon double bond of arylidene acetones and chalcones can be selectively reduced with benzeneselenol generated in situ by reacting O-(tert-butyl) Se-phenyl selenocarbonate with hydrochloric acid in ethanol. This mild, metal-free and experimentally simple reduction procedure displays considerable functional-group compatibility, products are obtained in good to excellent yields, and the use of toxic Se/CO mixture and NaSeH, or the smelly and air-sensitive benzeneselenol, is avoided. This journal is
- Ballarotto, Marco,Siciliano, Carlo,Temperini, Andrea
-
p. 33706 - 33717
(2020/10/22)
-
- Metal-free difunctionalization of alkynes to access tetrasubstituted olefins through spontaneous selenosulfonylation of vinylidene: Ortho -quinone methide (VQM)
-
A metal-free difunctionalization of alkynes to access tetrasubstituted olefins through spontaneous selenosulfonylation of vinylidene ortho-quinone methide (VQM) was described herein. The reaction was conducted under mild conditions without any catalysts or additives. Preliminary mechanism studies revealed that the formation of VQM was the key for this alkyne di-functionalization reaction. The reaction could be applied in the enantioselective asymmetric synthesis of axially chiral styrene. Furthermore, the selenosulfonylation adducts can be transformed into useful naphtho[2,1-b]furan and benzofuran scaffolds.
- Huang, Shengli,Chen, Zhili,Mao, Hui,Hu, Fangli,Li, Dongmei,Tan, Yu,Yang, Fengqing,Qin, Wenling
-
supporting information
p. 1121 - 1129
(2019/02/07)
-
- Rhodium-Catalyzed Carbene Transfer Reactions for Sigmatropic Rearrangement Reactions of Selenium Ylides
-
The rearrangement of selenium ylides is even today almost unexplored, although it would provide access to important organoselenium compounds with broad downstream applications. In this report, the first systematic study of sigmatropic rearrangement reactions of selenium ylides using a simple rhodium catalyst with catalyst loadings as low as 0.01 mol % is described. Selenium oxide pyrolysis of the rearrangement products gives access to important 1,1-disubstituted butadienes.
- Jana, Sripati,Koenigs, Rene M.
-
supporting information
p. 3653 - 3657
(2019/05/24)
-
- Atom Transfer Oxidative Radical Cascade of Aryl Alkynoates towards 1,1-Dichalcogenide Olefins
-
An oxidative trifunctionalization of aryl alkynoates has been devised via the chalcogenide radical triggered intramolecular 1,4-aryl migration/decarboxylation cascade to prepare 1,1-dichalcogenide tetrasubstituted alkenes in high yields (up to 98 %). This operationally simple reaction proceeds under metal-free conditions, can be executed on gram scale, and highlights formal 1,1-difunctionalization of alkynes. Synthetic potential of this protocol was demonstrated through a twofold cascade rearrangement to access highly conjugated tetra-selenylated alkenes along with a cross-dehydrogenative annulation to prepare fluorene derivative.
- Sahoo, Harekrishna,Ramakrishna, Isai,Mandal, Anup,Baidya, Mahiuddin
-
supporting information
p. 4549 - 4552
(2019/07/31)
-
- Iron(III)-catalyzed synthesis of selenoesters from α-amino carbonyl derivatives at room temperature
-
An Fe(III)-catalyzed efficient method has been developed for the synthesis of selenoester derivatives in high yields through the coupling of α-amino carbonyl/glycine derivatives and diselenides under ambient air. A library of benzoselenoate derivatives having a variety of substituents has been synthesized. A plausible reaction pathway has been predicted. Experimental results suggest that the reaction proceeds through a radical pathway. Operational simplicity, compatibility with various α-amino carbonyls and diselenides, high yields, fast reaction and mild reaction conditions are the notable advantages of this procedure. We have also shown the practical application of the synthesized selenoesters which is useful to generate peptide bonds in biological sciences.
- Chatterjee, Rana,Mukherjee, Anindita,Santra, Sougata,Zyryanov, Grigory V.,Majee, Adinath
-
-
- Acyl Selenyl Sulfides as the Precursors for Reactive Sulfur Species (Hydrogen Sulfide, Polysulfide, and Selenyl Sulfide)
-
Persulfides are receiving increased attention due to their links to hydrogen sulfide (H2S) and hydrogen polysulfide (H2Sn). Their close analogues selenyl sulfides (RSeSHs), however, have limited literature precedent, and their reactivity and possible role in biology are largely unknown. Here, we devised an acyl selenyl sulfide template to study RSeSH chemistry. Their stability and reactivity toward amines/thiols were studied. These compounds can produce H2S or H2S2 under different conditions, suggesting that RSeSHs are possible intermediates.
- Hamsath, Akil,Wang, Yingying,Yang, Chun-Tao,Xu, Shi,Ca?edo, Danica,Chen, Wei,Xian, Ming
-
p. 5685 - 5688
(2019/08/01)
-
- T BuOK-triggered bond formation reactions
-
Recently, inexpensive and readily available tBuOK has seen widespread use in transition-metal-free reactions. Herein, we report the use of tBuOK for S-S, S-Se, NN and CN bond formations, which significantly extends the scope of tBuOK in chemical synthesis. Compared with traditional methods, we have realized mild and general methods for disulfide, azobenzenes imine etc. synthesis.
- Xu, Yulong,Shi, Xiaonan,Wu, Lipeng
-
p. 24025 - 24029
(2019/08/13)
-
- Metal-free visible-light induced cyclization/substitution cascade reaction of alkyne-tethered cyclohexadienones and diselenides: Access to 5-hydroxy-3-selenyl-4a,8a-dihydro-2: H -chromen-6(5 H)-ones
-
A simple and efficient Se-radical triggered cyclization/substitution cascade reaction of alkyne-tethered cyclohexadienones to afford 5-hydroxy-3-selenyl-4a,8a-dihydro-2H-chromen-6(5H)-ones has been developed. This transformation via the 3,5-diselenyl-4a,8a-dihydro-2H-chromen-6(5H)-one intermediate followed by hydrolysis in the presence of CsOAc affords the desired product 3. The resulting products were tested for their in vitro anticancer activity using MTT assay, and compounds 3e and 3q showed potent cancer cell-growth inhibition activities.
- Ma, Xian-Li,Wang, Qian,Feng, Xi-Yuan,Mo, Zu-Yu,Pan, Ying-Ming,Chen, Yan-Yan,Xin, Mao,Xu, Yan-Li
-
supporting information
p. 3547 - 3551
(2019/07/09)
-
- Synthesis of Monofluoromethyl Selenoethers of Aryl and Alkyl from Organoselenocyanate via One-Pot Reaction
-
The first practical and feasible approach for the monofluoromethylselenolation of aryl and alkyl halides via one-pot multistep synthesis using KSeCN and ICFH2 is described. Good yields and broad functional group compatibility were obtained. The successful preparation of monofluoromethylselenolated drug-like compounds good practicability of this method. This protocol offered a number of new monofluoromethyl selenoethers, which would accelerate the use of such compounds in the areas of life science. (Figure presented.).
- Cao, Yuan,Jiang, Lvqi,Yi, Wenbin
-
p. 4360 - 4368
(2019/08/01)
-
- Metal-Free ipso -Selenocyanation of Arylboronic Acids Using Malononitrile and Selenium Dioxide
-
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
-
supporting information
p. 3758 - 3764
(2019/09/30)
-
- Design, synthesis and biological evaluation of novel semicarbazone-selenochroman-4-ones hybrids as potent antifungal agents
-
A series of novel 2,3-dihydro-4H-1-benzoselenin-4-one (thio)semicarbazone derivatives were designed and synthesized by using molecular hybridization approach. All the target compounds were characterized by HRMS and NMR and evaluated in vitro antifungal activity against five pathogenic strains. In comparison with precursor selenochroman-4-ones, the hybrid molecules in this study showed significant improvement in antifungal activities. Notably, compound B8 showed significant antifungal activity against other strains excluding Aspergillus fumigatus (0.25 μg/mL on Candida albicans, 2 μg/mL on Cryptococcus neoformans, 8 μg/mL on Candida zeylanoides and 2 μg/mL on fluconazole-sensitive strains of Candida albicans). Moreover, compounds B8, B9 and C2 also displayed most potent activities against four fluconazole-resistance strains. Especially the MIC values of the hybrid molecule B8 against fluconazole-resistant strains were in the range of 0.5–2 μg/mL. Therefore, the molecular hybridization approach in this study provided new ideas for the development of antifungal drug.
- Xu, Hang,Su, Xin,Liu, Xiao-qian,Zhang, Kai-peng,Hou, Zhuang,Guo, Chun
-
supporting information
(2019/10/19)
-
