Efficient halogenation of unsaturated organoaluminum compounds with sulfonyl halides

Ramazanov, Ilfir R.; Kadikova, Rita N.; Джемилев, У. М.

doi:10.1134/s1070428013030020

Cited by 7 publications

(8 citation statements)

References 21 publications

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“…In order to further study transformations of acetylenic compounds under the organoniobium synthesis conditions, we made attempts to develop efficient reagents for transformations of niobiacyclopropene intermediates. Previously, we have demonstrated that sulfonic acid derivatives, such as sulfonyl halides, sulfonic acid silyl esters, alkylthiosulfonates, organic disulfides and diselenides are efficient electrophilic reagents for the functionalization of organoaluminum compounds, such as 1-alkenylalanes, which can be used to prepare the corresponding alkenyl halides [ 57 ], alkenylsilanes [ 58 ], alkenyl sulphides [ 59 , 60 ] and alkenyl selenides [ 61 ] in high yields under mild conditions. We expected that sulfonyl halides would also be reactive toward niobiacyclopropene intermediate generated in this reaction.…”

Section: Resultsmentioning

confidence: 99%

NbCl5-Mg Reagent System in Regio- and Stereoselective Synthesis of (2Z)-Alkenylamines and (3Z)-Alkenylols from Substituted 2-Alkynylamines and 3-Alkynylols

et al. 2021

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The reduction of N,N-disubstituted 2-alkynylamines and substituted 3-alkynylols using the NbCl5–Mg reagent system affords the corresponding dideuterated (2Z)-alkenylamine and (3Z)-alkenylol derivatives in high yields in a regio- and stereoselective manner through the deuterolysis (or hydrolysis). The reaction of substituted propargylamines and homopropargylic alcohols with the in situ generated low-valent niobium complex (based on the reaction of NbCl5 with magnesium metal) is an efficient tool for the synthesis of allylamines and homoallylic alcohols bearing a 1,2-disubstituted double bond. It was found that the well-known approach for the reduction of alkynes based on the use of the TaCl5-Mg reagent system does not work for 2-alkynylamines and 3-alkynylols. Thus, this article reveals a difference in the behavior of two reagent systems—NbCl5-Mg and TaCl5-Mg, in relation to oxygen- and nitrogen-containing alkynes. A regio- and stereoselective method was developed for the synthesis of nitrogen-containing E-β-chlorovinyl sulfides based on the reaction of 2-alkynylamines with three equivalents of methanesulfonyl chloride in the presence of stoichiometric amounts of niobium(V) chloride and magnesium metal in toluene.

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Section: Resultsmentioning

confidence: 99%

NbCl5-Mg Reagent System in Regio- and Stereoselective Synthesis of (2Z)-Alkenylamines and (3Z)-Alkenylols from Substituted 2-Alkynylamines and 3-Alkynylols

et al. 2021

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“…Previously, we developed effective one-pot methods for the preparation of 1-alkenyl halides, 41 1-alkenylsilanes, 43 and 1-alkenyl sulfides 40 based on cross-coupling of 1-alkenylalanes with appropriate sulfonic acid derivatives: sulfonyl halides, substituted silyl sulfonates, and S-methyl methanesulfonothioate. Thus, 1-alkenylalanes are efficient substrates for the synthesis of various classes of organic compounds.…”

Section: Scheme 3 Zr-catalyzed Methylalumination Of Substituted 1-alkmentioning

confidence: 99%

“…Since deuterolysis demonstrates the presence of the intermediate organoaluminum species we have attempted to functionalize alkenylalane 1 with electrophilic reagents. We have previously shown that alkenylalanes, derived from the Zr-catalyzed methylalumination reaction of terminal and dialkylsubstituted alkynes along with the products of hydro-and cycloalumination of alkynes, successfully react with precursors of electrophilic reagents such as sulfonyl halides, organic disulfides, silyl esters of sulfonic acids, and S-methyl methanethiosulfonate to give the corresponding alkenyl halides, 41 alkenyl sulfides, 40,42 and alkenyl silanes 43 in high yields. Unfortunately, the above electrophiles were inert towards selenium-containing alkenylalanes 1 resulting from the Zr-catalyzed reaction of 1-alkynyl selenides with Et 3 Al.…”

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confidence: 99%

Zirconium-Catalyzed Alkyne Carbo- and Cycloalumination Reactions in Stereoselective Preparation of 1-Alkenyl Selenides

et al. 2017

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Supporting informationThe reagents were obtained from Sigma-Aldrich or Acros. Dichloromethane and hexane were distilled over P 2 O 5 . Organic diselenides were prepared by the reaction of elemental selenium with hydrazine hydrate and bromobenzene or bromoalkane under the action of sodium hydroxide solution in DMF [1]. The alkynyl selenides were prepared by the reaction of terminal alkynes with elemental selenium and bromoalkanes [2]. IR spectra were recorded on Bruker VE Vertex 70v spectrometer as liquid films or in Nujol and are reported in wavenumbers (cm -1 ).Nuclear magnetic resonance spectroscopy was performed on a Brucker Avance 400. The 1 H NMR spectra were recorded at 400 MHz and 13 C NMR spectra at 100 MHz in CDCl 3 . The chemical shifts are reported in ppm relative to tetramethylsilane (TMS) as the internal standard. The numbering of atoms in the 13 С and 1 H NMR spectra of the compounds A-F and 2a-f, 3b-e, 4a-e, 5b, 7a-f, 8ac is shown in Figures 1,2,3,4,5. Elemental analysis was performed using a Carlo-Erba CHN 1106 elemental analyser. Mass spectra were obtained on a Finnigan 4021 instrument. The yields were calculated from the isolated amount of 1-alkenyl selenides obtained from starting alkynes. All quantum-chemical calculations were performed using B3LYP/6-31G(d,p) basis set as implemented in Gaussian 09 software [3]. Preparation of alkynyl selenides A-F by the reaction of alkynyl lithium with elemental Se and bromoalkanes Figure 1The numbering of atoms in the 13 Сand 1 H-NMR spectra of the compounds A-F Butyl(hex-1-yn-1-yl)selenide (A)To a two-neck round-bottomed flask, under argon, containing a solution of hex-1yne (820 mg, 10 mmol) in THF (30 mL) at -78 o C was added to n-BuLi (4.0 mL of a 2.5M solution in hexane; 10 mmol). The reaction mixture was stirred for 30 min.After this the reaction was warmed to 0 o C and elemental selenium (800 mg; 10 mmol) was added. The reaction was allowed to stir at reflux for 5 h. After this time, the reaction was cooled to room temperature and then the butyl bromide (685 mg, 5 mmol) was added. The reaction mixture was allowed to stir at room temperature for additional 12 h. After this time, the mixture was diluted with ethyl acetate (20 mL) and washed with saturated aqueous NH 4 Cl (20 mL) and water (3×20 mL). The organic phase was separated, dried over MgSO 4 . Evaporation of solvent and purification of the residue by column chromatography (silica gel, petroleum ether) gave a colourless oil; yield: 1800 mg (83%); R f = 0.72 (petroleum ether). Butyl(hept-1-yn-1-yl)selenide (B)Using the procedure described above hept-1-yne (960 mg, 10 mmol) and 1bromobutane (685 mg, 5 mmol) gave a crude product that was purified by flash chromatography (silica gel, petroleum ether) to afford a colorless oil; yield: 1825 mg (79%); Rf = 0.77 (petroleum ether).Butyl(oct-1-yn-1-yl)selenide (C)Using the procedure described above hept-1-yne (960 mg, 10 mmol) and 1bromobutane (685 mg, 5 mmol) gave a crude product that was purified by flash chromatography (silica gel, petroleum ether) to a...

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“…Earlier, we reported that sulfonic acid derivatives are efficient for a functionalization of various alkenylalanes. Efficient one-pot methods for alkenylalane halogenation with sulfonyl halides have been developed, 22 as well as silylation methods using trialkylsilyl sulfonates. 23 Meanwhile, recently we have developed a new method for sulfanylation of organoaluminum compounds on treatment with organic disulfides, which is suitable for the selective preparation of alkenyl sulfides in high yields in one step under mild conditions.…”

Section: Paper Syn Thesismentioning

confidence: 99%

“…23 The silylation of 2,3-dialkyl-substituted aluminacyclopent-2-enes on treatment with organosilicon esters of sulfonic acids also involves the Al-C(sp 3 ) bond of the ring. 22 Thus, methyl thiosulfonate provided a chemoselective functionalization of the Al-C(sp 2 ) bond of cyclic α,β,β-trisubstituted vinylalanes.…”

Section: Paper Syn Thesismentioning

confidence: 99%

Zirconocene Catalysis in Organoaluminum Synthesis of 1-Alkenyl Sulfones and Sulfides

et al. 2016

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Efficient halogenation of unsaturated organoaluminum compounds with sulfonyl halides

Cited by 7 publications

References 21 publications

NbCl5-Mg Reagent System in Regio- and Stereoselective Synthesis of (2Z)-Alkenylamines and (3Z)-Alkenylols from Substituted 2-Alkynylamines and 3-Alkynylols

NbCl5-Mg Reagent System in Regio- and Stereoselective Synthesis of (2Z)-Alkenylamines and (3Z)-Alkenylols from Substituted 2-Alkynylamines and 3-Alkynylols

Zirconium-Catalyzed Alkyne Carbo- and Cycloalumination Reactions in Stereoselective Preparation of 1-Alkenyl Selenides

Zirconocene Catalysis in Organoaluminum Synthesis of 1-Alkenyl Sulfones and Sulfides

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