Synthesis of Trimethylsilylpropynoyl Chloride

Медведева, А. С.; Andreev, M. V.; Сафронова, Л. П.; Афонин, А. В.

doi:10.1007/s11178-005-0367-8

Cited by 17 publications

(20 citation statements)

References 11 publications

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“…IR spectrum, ν, cm -1 : 1730 (C=O), 2160 (C≡C). 1 29 mmol) of amine II, and 0.3 ml of 0.8% hydrochloric acid (5 mol %) in 1 ml of acetonitrile was kept for 7 days at 25°C with intermittent shaking. The solvent was removed under reduced pressure, and the solid residue was analyzed by 1 H NMR spectroscopy.…”

Section: -(2-pyridyl)-2-trimethylsilylethynyl-12-dihydropyridine-3mentioning

confidence: 99%

“…We previously showed that the triple bond in heteroelement-containing propynals R 3 EC≡CHO (E = Si, Ge) in the absence of a catalyst is inactive toward N-nucleophiles [1]. Primary amines add to silicon-and germanium-containing propynals and their carbon analog, 3-tert-butylpropynal, chemoselectively at the aldehyde group to give the corresponding Schiff bases in almost quantitative yield [2].…”

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New Microwave-Assisted Reaction of 3-Trimethylsilylpropynal with 2-Aminopyridine

et al. 2005

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Section: -(2-pyridyl)-2-trimethylsilylethynyl-12-dihydropyridine-3mentioning

confidence: 99%

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New Microwave-Assisted Reaction of 3-Trimethylsilylpropynal with 2-Aminopyridine

et al. 2005

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“…This approach was partially reviewed in [2]. The presence of a trimethylsilyl group at triple C≡C bond stabilizes the latter so that it becomes inactive toward nucleophiles [3], organometallic compounds, and transition metal catalysts in various synthetic transformations [4]; as a result, regioselective cycloaddition of azides at the triple bond of various trimethylsilylalkynes becomes possible [5], the stability of compounds increases, and their solubility in organic solvents is improved.…”

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“…A mixture of 0.47 mmol of amide Ib-Ig,3.4 mg (5 mol %) of KF-Al 2 O 3 , and 5 ml of methanol was stirred for 20 min at room temperature. The mixture was then treated with 1 ml of 5% hydrochloric acid and extracted with diethyl ether (in the synthesis of IIb-IId) or chloroform (IIe-IIg), and the extract was dried over MgSO 4 and evaporated under reduced pressure.…”

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Highly efficient desilylation of 3-trimethylsilylprop-2-ynamides by the action of KF-Al2O3

2011

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A highly effective procedure has been developed for desilylation of 3-trimethylsilylprop-2-ynamides in the presence of KF-Al 2 O 3 as catalyst. The corresponding terminal prop-2-ynamides were obtained in high yield in methanol at 25°C using 5 mol % of the catalyst (reaction time 20 min). Rise in temperature leads to the formation of Z,E-3-methoxyprop-2-enamides or 3,3-dimethoxypropanamides as a result of tandem desilylation-addition of methanol, depending on the conditions. The synthetic strategy silylation-desilylation of triple bond is widely used in fine organic synthesis, in particular in total syntheses of highly efficient natural antibiotics [1]. This approach was partially reviewed in [2]. The presence of a trimethylsilyl group at triple C≡C bond stabilizes the latter so that it becomes inactive toward nucleophiles [3], organometallic compounds, and transition metal catalysts in various synthetic transformations [4]; as a result, regioselective cycloaddition of azides at the triple bond of various trimethylsilylalkynes becomes possible [5], the stability of compounds increases, and their solubility in organic solvents is improved.Desilylation of acetylenic compounds can be performed with the use of various reagents, among which such bases as alkali metal hydroxides [6], alkoxides [7], and carbonates [8] in protophylic solvents, as well as potassium [9] and ammonium fluorides [10] are used most frequently. We recently showed that successful desilylation may be achieved with the aid of even weak bases generated in protic medium from metal oxides (PbO 2 , MnO 2 , Co 2 O 3 , Ni 2 O 3 ) [11].Despite diversity of desilylating agents, published data on desilylation of silicon-containing acetylenic compounds with an activated triple bond are few in number. Desilylation of such compounds requires mild conditions, taking into account the possibility for undesirable addition of alcohol or water (used as solvent) at the terminal triple bond in the resulting alkynes by the action of base in protophilic medium.In the present work we developed an efficient procedure for desilylation of trimethylsilylacetylenes having an activated triple bond. 3-Trimethylsilylprop-2-ynamides Ia-Ig were selected as substrates, and KFAl 2 O 3 , as reagent. Solid-phase desilylation of trimethylsilylalkynes under microwave irradiation required excess KF-Al 2 O 3 (4 equiv) [12]. There are no published data on desilylation of trimethylsilylacetylene derivatives with an activated triple bond by the action of KF-Al 2 O 3 . O Ia-Ig KF-Al 2 O 3 (5 mol %) MeOH, 25°C, 20 min HC NR 1 R 2 O IIa-IIg R 1 = H, R 2 = H (a), Ph (b), PhCH 2 (c), 2,5-Cl 2 C 6 H 3 (d), 3-BrC 6 H 4 (e), HOCH 2 CMe 2 (f); R 1 R 2 N = morpholino (g).

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“…The presence of a silicon or germanium atom at the triple bond stabilizes propynal molecule and adducts derived therefrom, whereas subsequent demetalation under mild conditions could produce analogs with terminal triple bond. We previously showed that silicon-and germanium-containing propynals and their carbon analog react with primary amines in the absence of a catalyst chemoselectively at the aldehyde group with formation of the corresponding Schiff bases [2]. However, the nature of primary amine and reaction conditions could affect to a considerable extend both chemoselectivity of the addition reaction and structure of the products.…”

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Chemoselective reactions of trimethylsilylpropynal with aminopyrimidines and amino acid esters

et al. 2011

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Highly efficient chemoselective 1,2-addition of 2-aminopyrimidines and D,L-amino acid esters to substituted propynals was performed. Acid-catalyzed addition of 2-aminopyrimidine and 2-amino-4-methylpyrimidine to trimethylsilyl-and phenylpropynals gave previously unknown acetylenic aminals. Reactions of α-amino acid methyl esters (alanine and lysine) with trimethylsilylpropynal led to the formation of new aza enynes in high yield. Regardless of the reactant ratio, trimethylsilylpropynal reacted with lysine at both amino groups with formation of bis-aza enyne.Propynals occupy an important place among acetylene derivatives. They are ambident bielectrophiles and are used as building blocks in fine organic synthesis and total syntheses of highly effective antibiotics of natural origin, as well as in the design of promising materials possessing magnetic or electrooptical properties [1]. Heteroatom-containing propynals attract specific attention in the chemistry of α,β-acetylenic aldehydes. The presence of a silicon or germanium atom at the triple bond stabilizes propynal molecule and adducts derived therefrom, whereas subsequent demetalation under mild conditions could produce analogs with terminal triple bond. We previously showed that silicon-and germanium-containing propynals and their carbon analog react with primary amines in the absence of a catalyst chemoselectively at the aldehyde group with formation of the corresponding Schiff bases [2]. However, the nature of primary amine and reaction conditions could affect to a considerable extend both chemoselectivity of the addition reaction and structure of the products. For example, the addition of 2-aminoethanethiol to trimethylsilyl(or triethylgermyl)propynal occurs chemoselectively at the carbonyl group with formation of the corresponding Schiff bases or their cyclization products, 2-[3-trimethylsilyl(or triethylgermyl)prop-2-yn-1-yl]-1,3-thiazolidines, depending on the conditions [3]. It was also found that reactions of heteroelement-containing propynals with nitrogencentered 1,3-binucleophiles can involve one or two reaction centers in the propynal and binucleophile. 2-Aminopyridine reacted with trimethylsilyl(or triethylgermyl)propynal generated in situ under conditions of tandem oxidation-amination of the corresponding alcohols by the action of MnO 2 -SiO 2 under microwave (MW) irradiation to produce imidazo-[1,2-a]pyridine-3-carbaldehyde [4]. Cascade assembly of the product involved the triple bond in the propynal and both nucleophilic centers in 2-aminopyridine.Acid-catalyzed reaction of trimethylsilylpropynal with 2-aminopyridine followed previously unknown scheme with formation of N-(pyridin-2-yl)-2-(trimethylsilylethynyl)-1,2-dihydropyridine-3,5-dicarbaldehyde in high yield. Both reaction center in the propynal molecule participated in this process, and the resulting heterocycle was built of three aldehyde molecules and one amine molecule [5]. Analogous reaction of phenylpropynal with 2-aminopyridine resulted in self-assembly of hitherto unknown 3-[pyridin...

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Synthesis of Trimethylsilylpropynoyl Chloride

Cited by 17 publications

References 11 publications

New Microwave-Assisted Reaction of 3-Trimethylsilylpropynal with 2-Aminopyridine

New Microwave-Assisted Reaction of 3-Trimethylsilylpropynal with 2-Aminopyridine

Highly efficient desilylation of 3-trimethylsilylprop-2-ynamides by the action of KF-Al2O3

Chemoselective reactions of trimethylsilylpropynal with aminopyrimidines and amino acid esters

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