81763-73-7Relevant academic research and scientific papers
Synthesis of (E)-β-Selenovinyl Sulfones through a Multicomponent Regio- and Stereospecific Selenosulfonation of Alkynes with Insertion of Sulfur Dioxide
Sun, Kai,Shi, Zuodong,Liu, Zhenhua,Luan, Baixue,Zhu, Jiali,Xue, Yanru
supporting information, p. 6687 - 6690 (2018/11/21)
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.
Metal-free selenosulfonylation of alkynes: Rapid access to β-(seleno)vinyl sulfones via a cationic-species-induced pathway
Sun, Kai,Wang, Xin,Fu, Fangfang,Zhang, Chong,Chen, Yao,Liu, Lin
, p. 1490 - 1493 (2017/05/10)
A novel and convenient method has been developed for the 1,2-selenosulfonylation of alkynes under metal-free conditions. The reaction avoids the need for the pre-prepared Se-S reagents, providing facile access to a series of β-(seleno)vinyl sulfones with
Copper-Catalyzed Three Component Regio- and Stereospecific Selenosulfonation of Alkynes: Synthesis of (E)-β-Selenovinyl Sulfones
Liu, Yang,Zheng, Guangfan,Zhang, Qian,Li, Yan
, p. 2269 - 2275 (2017/02/26)
A copper-catalyzed highly regio- and stereospecific selenosulfonation of alkynes with arylsulfonohydrazides and diphenyl diselenide has been developed. This novel three component reaction proceeds under very mild conditions and with a broad scope of substrates, providing a wide range of (E)-β-selenovinyl sulfones in good to excellent yields.
1,3-Dipolar cycloadditions of acetylenic sulfones in solution and on solid supports
Gao, Detian,Zhai, Huimin,Parvez, Masood,Back, Thomas G.
, p. 8057 - 8068 (2008/12/22)
(Chemical Equation Presented) Several representative acetylenic sulfones were immobilized on a polymer support derived from Merrifield resin by means of ester linkers that were used to couple free carboxylic acid groups on the solid support with benzylic hydroxyl functions on the arylsulfonyl moieties of the acetylenes. Several examples of reversed ester linkers, using Merrifield resin directly, were also successfully prepared. The 1,3-dipolar cycloadditions of the solid-supported acetylenic sulfones were investigated with a series of 1,3-dipoles, including benzyl azide, ethyl diazoacetate, diazomethane, as well as representative nitrile oxides, nitrile imines, nitrile ylides, nitrones, azomethine imines, azomethine ylides, munchnones, and sydnones. In general, analogous cycloadditions were also performed with acetylenic sulfones in solution phase for comparison. The cycloadditions typically afforded good to excellent yields of the desired products in both solution and solid phase, although the latter reactions sometimes required more vigorous conditions. Except in the case of benzyl azide and diazo compounds, where mixtures of regioisomers were obtained, the other 1,3-dipoles reacted with high regioselectivity and afforded essentially unique regioisomers. Cleavage of the products from the resin was smoothly effected by alkaline hydrolysis, while several attempts at reductive desulfonylation with sodium amalgam or samarium diiodide-HMPA resulted in N-O or C-O scission, in addition to cleavage from the polymer. The method provides access to a number of important classes of heterocycles, including variously substituted and functionalized triazoles, pyrazoles, 1,2-oxazoles, pyrroles, as well as their dihydro and bicyclic analogues. The success of the cycloadditions on polymer supports paves the way to future investigations of sequential transformations leading to libraries of useful heterocycles.
Solid-phase synthesis of β-keto sulfones
Qian, Hao,Huang, Xian
, p. 1934 - 1936 (2007/10/03)
A novel method for the preparation of β-keto-sulfones through the use of organoselenium reagents in the solid phase by polystyrene-supported benzeneselenosulfonate or tolueneseleno-sulfonate with acetylenes has been developed. Georg Thieme Verlag Stuttgart.
Free radical reaction of sodium arenesulfinates with acetylenes: New regio- and stereoselective preparation of (E)-β-(phenylseleno)vinyl sulfones
Huang, Xian,Xu, Qing,Liang, Chun-Gen,He, Qi-Weng
, p. 1243 - 1249 (2007/10/03)
Free radical reaction of terminal acetylenes with sodium arenesulfinates and diphenyl diselenide in aqueous acetic acid affo31yrded high yields of the regio- and stereoselective (E)-β-(phenylseleno)vinyl sulfones.
Highly stereoselective three-component reactions of phenylselenomagnesium bromide, acetylenic sulfones, and saturated aldehydes/ketones or α,β-unsaturated enals or enones
Huang, Xian,Xie, Meihua
, p. 8895 - 8900 (2007/10/03)
β-Phenylseleno-α-tolylsulfonyl-substituted alkenes were synthesized via the three-component conjugate-nucleophilic addition of acetylenic sulfones, phenylselenomagnesium bromide, and carbonyl compounds, such as aldehydes, aliphatic ketones, or α-unsaturated enals or enones. The reaction is highly regio- and stereoselective with moderate to good yields. Functionalized allylic alcohols were obtained in the case of aldehydes and aliphatic ketones. In the case of α,β-unsaturated enones, functionalized allylic alcohols or functionalized γ,δ-unsaturated ketones were obtained, depending on the structures of the ketones.
A convenient new route to piperidines, pyrrolizidines, indolizidines, and quinolizidines by cyclization of acetylenic sulfones with β- and γ-chloroamines. Enantioselective total synthesis of indolizidines (-)-167B, (-)-209D, (-)-209B, and (-)-207A
Back, Thomas G.,Nakajima, Katsumasa
, p. 4543 - 4552 (2007/10/03)
The methyl esters of (L)-phenylalanine and (L)-methionine underwent conjugate additions via their free amino groups to 1-(p-toluenesulfonyl)hexyne, followed by intramolecular acylation of the corresponding enamide anions and tautomerization to afford 2-benzyl-5-n-butyl-3-hydroxy-4-(p-toluenesulfonyl)pyrrole and 5-n-butyl-3-hydroxy-2-(2-methylthioethyl)-4-(p-toluenesulfonyl)pyrrole, respectively. The conjugate additions of a series of acyclic and cyclic secondary β- and γ-chloroamines to acetylenic sulfones proceeded similarly under mild conditions. The resulting adducts were deprotonated with LDA in THF at -78 °C, and the resulting sulfone-stabilized carbanions underwent intramolecular alkylation to afford cyclic enamine sulfones. Thus, acyclic γ-chloroalkylbenzylamines afforded the corresponding 2- or 2,6-disubstituted piperidines, while 2-(chloromethyl)-pyrrolidines, 2-(2-chloroethyl)pyrrolidines, 2-(chloromethyl)piperidines, and 2-(2-chloroethyl)-piperidines produced the corresponding 3-substituted pyrrolizidines, 5- or 3-substituted indolizidines, and 4-substituted quinolizidines, respectively. 8-Methyl-5-substituted indolizidines were also prepared from the appropriate methyl-substituted chloroamine precursor. Enantioselective syntheses were achieved by employing chiral chloroamines derived from amino acids or other enantiopure precursors. Further transformations of several of the products provided concise syntheses of four dendrobatid alkaloids. Thus, reduction of (8aS)-5-n-propyl-6-(p-toluenesulfonyl)-Δ-indolizidine with sodium cyanoborohydride in trifluoroacetic acid, followed by reductive desulfonylation, afforded (-)-indolizidine 167B. The corresponding 5-n-hexyl derivative similarly produced (-)-indolizidine 209D, while (-)-(8R,8aS)-8-methyl-5-n-pentyl-6-(p-toluenesulfonyl)-Δ5,6-indolizidine furnished (-)-indolizidine 209B. Finally, the similar reduction and debenzylation of (-)-(8R,8aS)-5-(2-benzyloxyethyl)-8-methyl-6-(p-toluenesulfonyl)-Δ-indolizid ine produced the corresponding 5-hydroxyethyl indolizidine. This was subjected to chlorination of the alcohol group with thionyl chloride and substitution with a higher order allyl cuprate reagent to afford (-)-indolizidine 207A.
Selenosulfonation of Acetylenes: Preparation of Novel β-(Phenylseleno)vinyl Sulfones and Their Conversion to Acetylenic and β-Functionalized Sulfones
Back, Thomas G.,Collins, Scott,Kerr, Russell G.
, p. 3077 - 3084 (2007/10/02)
The 1,2-additions of Se-phenyl p-tolueneselenosulfonate (1) to acetylenes under mild conditions afford β-(phenylseleno)vinyl sulfones 3, generally in high yields.The reaction is highly regioselective (anti-Markovnikov) and stereoselective (anti) and proceeds via a free-radical chain mechanism initiated by the thermolysis of the selenosulfonate.The oxidation of β-(phenylseleno)vinyl sulfones with m-chloroperbenzoic acid generates the corresponding selenoxides 4, which undergo syn or base-catalyzed elimination to furnish acetylenic sulfones 5.Base-catalyzed alcoholyses of selenoxides 4 in methanol or ethylene glycol produce β-keto sulfone ketals 8 or 10, respectively.Free β-keto sulfones 11 are formed by the acid-catalyzed hydrolysis of the corresponding β-(phenylseleno)vinyl sulfones 3.
Addition of Phenyl Areneselenosulphonates to Acetylenes: a Route to Acetylenic Sulphones
Miura, Takashi,Kobayashi, Michio
, p. 438 - 439 (2007/10/02)
Treatment of phenyl areneselenosulphonates (1) with terminal acetylenes resulted in the formation of β-(phenylseleno)vinyl sulphones (2), which on treatment with excess of hydrogen peroxide in tetrahydrofuran at room temperature gave acetylenic sulphones
