- Unusual Application for Phosphonium Salts and Phosphoranes: Synthesis of Chalcogenides
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A novel strategy for the synthesis of sulfides and selenides from phosphonium salts and thio- or selenesulfonates, commercially available compounds, is described. When phosphoranes were used in the reaction, different products were obtained. The methodology does not require the use of metals, reactive species, or anhydrous conditions to be performed.
- Moura, Igor M. R.,Tranquilino, Arisson,Sátiro, Barbara G.,Silva, Ricardo O.,De Oliveira-Silva, Diogo,Oliveira, Roberta A.,Menezes, Paulo H.
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p. 5954 - 5964
(2021/05/04)
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- Visible-light-driven radical 1,3-addition of selenosulfonates to vinyldiazo compounds
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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
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p. 6652 - 6658
(2021/09/10)
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- Alkene: Versus alkyne reactivity in unactivated 1,6-enynes: Regio-And chemoselective radical cyclization with chalcogens under metal-And oxidant-free conditions
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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
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p. 2288 - 2300
(2020/04/21)
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- Electrochemical Oxidative Cross-Coupling Reaction to Access Unsymmetrical Thiosulfonates and Selenosulfonates
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The electrochemical oxidative cross-dehydrogenative coupling of arylsulfinic acids with thiophenols was achieved via a radical process. A wide range of arylsulfinic acids and substituted thiophenols were found to be tolerated, providing unsymmetrical thio
- Zhang, Xiaofeng,Cui, Ting,Zhang, Yanghao,Gu, Weijin,Liu, Ping,Sun, Peipei
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p. 2014 - 2019
(2019/03/26)
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- Organocatalytic Enantioselective Selenosulfonylation of a C-C Double Bond to Form Two Stereogenic Centers in an Aqueous Medium
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Organocatalytic selenosulfonylation of the C-C double bond of α,β-unsaturated ketones to construct two contiguous stereogenic centers in an aqueous medium was described. A series of α-selenyl and β-sulfonyl ketones with various functional groups were synthesized in good yields and enantioselectivities with saturated NaCl solution as the solvent. In addition, this protocol had been successfully scaled up to a decagram scale via a simple workup procedure.
- Chen, Zhili,Hu, Fangli,Huang, Shengli,Zhao, Zhengxing,Mao, Hui,Qin, Wenling
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p. 8100 - 8111
(2019/06/17)
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- Metal-free difunctionalization of alkynes to access tetrasubstituted olefins through spontaneous selenosulfonylation of vinylidene: Ortho -quinone methide (VQM)
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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
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supporting information
p. 1121 - 1129
(2019/02/07)
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- Visible light-induced co- or cu-catalyzed selenosulfonylation of alkynes: Synthesis of β-(seleno)vinyl sulfones
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A visible light-induced Co- or Cu-catalyzed selenosulfonylation of alkynes for the synthesis of β-(seleno)vinyl sulfones is demonstrated. This method utilizes a low-cost cobalt salt or metal copper as the catalysts. The reaction goes through a photoinduced free radical addition of selenosulfonates to alkynes for the 1,2-selenosulfonylation of alkynes under mild conditions.
- Ji, Shun-Jun,Wang, Shun-Yi,Xu, Pei,Zhang, Rong
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- Synthesis of (E)-β-Selenovinyl Sulfones through a Multicomponent Regio- and Stereospecific Selenosulfonation of Alkynes with Insertion of Sulfur Dioxide
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A novel and practical method for the selenosulfonation of alkynes with the insertion of sulfur dioxide has been developed. A series of β-(seleno)vinyl sulfones with high levels of regio- and stereoselectivity have been prepared. The key features of this reaction include a broad substrate scope, excellent functional-group tolerance, and amenability to scale-up synthesis. A plausible radical mechanism is proposed to illustrate this reaction.
- Sun, Kai,Shi, Zuodong,Liu, Zhenhua,Luan, Baixue,Zhu, Jiali,Xue, Yanru
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p. 6687 - 6690
(2018/11/21)
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- Cobalt bis(acetylacetonate)–tert-butyl hydroperoxide–triethyl-silane: A general reagent combination for the Markovnikov-selective hydrofunctionalization of alkenes by hydrogen atom transfer
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We show that cobalt bis(acetylacetonate) [Co(acac)2], tert-butyl hydroperoxide (TBHP), and triethylsilane (Et3SiH) constitute an inexpensive, general, and practical reagent combination to initiate a broad range of Markovnikov-selective alkene hydrofunctionalization reactions. These transformations are believed to proceed by cobalt-mediated hydrogen atom transfer (HAT) to the alkene substrate, followed by interception of the resulting alkyl radical intermediate with a SOMOphile. In addition, we report the first reductive couplings of unactivated alkenes and aryldiazonium salts by an HAT pathway. The simplicity and generality of the Co(acac)2–TBHP–Et3SiH reagent combination suggests it as a useful starting point to develop HAT reactions in complex settings.
- Ma, Xiaoshen,Herzon, Seth B.
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supporting information
p. 2259 - 2265
(2018/09/14)
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- Oxidative coupling of dichalcogenides with sodium sulfinates via copper-catalyzed cleavage of s-s and se-se bonds
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A copper-catalyzed sulfonylation of disulfides was achieved using sodium sulfinates in air. The reaction formed various sulfur-sulfone bonds efficiently and afforded thiosulfonates in good yields. Selenosulfonates could also be prepared with this procedure. Furthermore, both chalcogenide groups on the dichalcogenides were available in these reactions.
- Taniguchi, Nobukazu
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p. 1764 - 1770
(2015/02/19)
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- Hypervalent iodine in synthesis X V III : Synthesis of selenosulfonates using a one pot reaction of diaryl diselenides, sodium sulfinates and [bis(trifluoroacetoxy)iodo] benzene
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A one pot reaction to synthesis selenosulfonates is reported.
- Chen, Da-Wei,Chen, Zhen-Chu
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p. 7637 - 7638
(2007/10/02)
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- A novel convenient synthesis of selenosulfonates
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Sodium sulfonate reacts smoothly with areneselenium cations, which are produced in situ by reacting diaryl diselenides with peroxydisulphate, to give selenosulfonates in good yields.
- Wang,Huang
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p. 2817 - 2820
(2007/10/02)
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- The free-radical cyclization reaction of 1,6-dienes with selenosulfonate
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A sulfonyl radical induced addition-cyclization reaction of 1,6-dienes with p-tolyl benzeneselenosulfonate giving functionalized cyclopentane system is described.
- Chuang
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p. 3151 - 3158
(2007/10/02)
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- On The Reactions of Benzeneseleninic Anhydride With Monosubstituted Hydrazones. Evidence for Radical Pathways.
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The known oxidation of mono-substituted hydrazones by benzeneseleninic anhydride has been studied using 77Se and 13C NMR spectroscopy.The intermediates in the reaction have been identified.Good evidence that certain steps in these reactions are radical in character has been secured.
- Barton, Derek H. R.,Okano, Takashi,Parekh, Shyamal I.
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p. 1823 - 1836
(2007/10/02)
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- REACTIONS OF SULFOHYDRAZIDES WITH BENZENESELENIC ACID, SELENIUM HALIDES, AND SULFUR HALIDES. A CONVENIENT PREPARATION OF SELENOSULFONATES AND THIOSULFONATES
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The oxidation of sulfohydrazides with benzeneselenic acid provides an efficient and convenient preparation of selenosulfonates.Se-Phenyl p-tolueneselenosulfonates was also produced in good to excellent yield from the reaction of p-toluenesulfohydrazide with PhSeCl, PhSeBr, or PhSeCl3.Sulfohydrazide react with sulfenyl halides or with PhSBr3 to produce thiosulfonates generally high yield.The treatment of p-toluenesulfohydrazide with benzenetellurinic acid, PhTeCl3, or PhTeBr3, afforded only diphenyl ditelluride and not the corresponding tellerosulfonate.
- Back, Thomas G.,Collins, Scott,Krishna, M. Vijaya
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- Oxidation of 1,1-disubstituted hydrazines with benzeneseleninic acid and selenium dioxide. Facile preparation of tetrazenes
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Various 1,1-disubstituted hydrazines were oxidized with benzeneseleninic acid in methanol, generally producing the corresponding tetrazenes in high yield.Studies of the by-products of the reaction, of the effects of protic vs. aprotic solvents, and trapping experiments suggest that N-aminonitrenes are unlikely intermediates in this oxidation.An alternative mechanism involving a Pummerer-like reaction of seleninamides derived from the hydrazines is proposed.Tetrazene formation fails when the hydrazine precursor contains an aryl or p-toluenesulfonyl substiuent, or when it is highly hindered.Selenium dioxide may be employed as the oxidant instead of the seleninic acid, but is generally less efficacious in achieving high tetrazene yields.
- Back, Thomas G.,Kerr, Russell G.
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p. 2711 - 2718
(2007/10/02)
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- Se-Phenyl Areneselenosulfonates: Their Facile Formation and Striking Chemistry
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Benzeneseleninic acid reacts rapidly at 0 deg C with aromatic sulfinic acids according to the stoichiometry of eq 3 to form Se-phenyl arenesulfonates, PhSeSO2Ar (2), in high yield.In contrast to thiosulfonates, PhSSO2Ar, areneselenosulfonates are extremely photosensitive and undergo quite rapid photodecomposition.The principal products of this photodecomposition are the sulfonic anhydride, ArSO2OSO2Ar, and diphenyl diselenide.In the presence of added alkenes the facile photodissociation of 2 can be used to initiate a free-radical chain reaction that results in the addition of 2 to the alkene to form β-phenylseleno sulfones in good yield.The β-phenylseleno sulfones can be converted to synthetically useful α,β-unsaturated sulfones by oxidation of the β-phenylseleno group to the corresponding selenoxide and subsequent elimination of PhSeOH.Photoaddition of 2 to 2,5-norbornadiene to 5-(phenylseleno)-exo-3-nortricyclyl aryl sulfone as the almost exclusive product, while photoaddition to 1,5-cyclooctadiene gives a mixture of approximately equal amounts of the 1,2-adduct, 5-(phenylseleno)-6-arenesulfonyl-1-cyclooctene, and the product of transannular addition, 6-(phenylseleno)-exo-2-arenesulfonyl-cis-bicyclooctane.Besides their extraordinary ease of photodissociation, compounds 2 also react extremely readily with nucleophiles: Nu- + PhSeSO2Ar -> PhSeNu + ArSO2-.Kinetic studies show that the reactivity of PhSeSO2Ar with cyanide ion in such a reaction is 70000 times larger than the reactivity of the corresponding thiosulfonate, PhSSO2Ar.
- Gancarz, Roman A.,Kice, John L.
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p. 4899 - 4906
(2007/10/02)
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- Selenosulfonation: Boron Trifluoride Catalyzed or Thermal Addition of Selenosulfonates to Olefins. A Novel Regio- and Stereocontrolled Synthesis of Vinyl Sulfones.
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Se-Phenyl areneselenosulfonates 1 add to a variety of olefins to produce β-phenylseleno sulfones 2.The reaction may be performed in the presence of boron trifluoride etherate to produce chiefly or exclusively Markovnikov products arising from a stereospecific anti addition.Alternatively, the addition may be thermally induced to afford anti-Markovnikov products generated by a nonstereospecific free-radical process.The two modes of addition achieve complementary regiospecificity.The β-phenylseleno sulfones are converted in high yield to vinyl sulfones by stereospecific oxidation-elimination with m-chloroperbenzoic acid.
- Back, Thomas G.,Collins, Scott
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p. 3249 - 3256
(2007/10/02)
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- A convenient synthesis of selenolsulfonates from the oxidation of sulfonhydrazides with benzeneseleninic acid
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The reaction of sulfonhydrazides with benzeneseleninic acid furnishes selenolsulfonates in high yield.
- Back, Thomas G.,Collins, Scott
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p. 2213 - 2214
(2007/10/02)
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- THE REACTION OF SULFINIC ACIDS WITH BENZENESELENINIC ACID
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Aromatic sulfinic acids are rapidly oxidized at 0 deg C by benzeneseleninic acid, setting in motion a reaction sequence whose final products are (a) the arenesulfonate salt of benzeneseleninic acid (2) and (b) the Se-phenyl areneselenosulfonate (1).
- Gancarz, Roman A.,Kice, John L.
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p. 1697 - 1700
(2007/10/02)
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