[2+2] Cycloaddition of electron-poor acetylenes to (E)-3-dimethylamino-1-heteroaryl-prop-2-en-1-ones: synthesis of highly functionalized 1-heteroaroyl-1,3-butadienes

Bezenšek, Jure; Kolesa, Tanja; Grošelj, Uroš; Wagger, Jernej; Stare, Katarina; Meden, Anton; Svete, Jurij; Stanovnik, B.

doi:10.1016/j.tetlet.2010.04.106

Cited by 39 publications

(14 citation statements)

References 33 publications

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“…The cycloadditions are supposed to proceed analogously as reported earlier for cycloadditions of electron-poor acetylenes to acyclic enaminones (Scheme 2). 12,13 In the reaction of enaminone 1b with DMAD (2), besides the main product 3b (yellow crystals) also a side product (w0.5%) (red crystals) was formed. The structure of this product was determined by X-ray analysis to be (S*,E)-trimethyl 11-(dimethylamino)-4,10-dioxobicyclo[5.3.1]undec-1(11),2,8-triene-2,8,9-tricarboxylate (10).…”

Section: Resultsmentioning

confidence: 99%

“…Mp¼227.0e230.2 C. 1 naphthalene); 7.26e7.32 (2H, m, naphthalene); 7.42 (1H, ddd, J 1 ¼2.6 Hz, J 2 ¼6.6 Hz, J 3 ¼8.1 Hz, naphthalene). 13 4.3. X-ray structure analysis for compounds 3b, 3c, 4c, 4d, 4e, 10 and 12…”

Section: General Procedures For the Reactions Of Endocyclic Enaminonesmentioning

confidence: 99%

“…10,11 Recently, polysubstituted butadienes have been prepared by microwave-assisted [2þ2] cycloadditions of enaminones to electron-poor acetylenes. 12,13 Polysubstituted aminobutadienes, prepared by this procedure, are suitable for the preparation of polysubstituted pyridine derivatives. They also represent a group of isomeric intermediates in regard to the aminobutadienes prepared via the Michael addition in the BohlmanneRahtz synthesis of pyridine derivatives.…”

Section: Introductionmentioning

confidence: 99%

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[2+2] Cycloadditions of electron-poor acetylenes to endocyclic enaminones: ring-expansion reactions

et al. 2015

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Section: Resultsmentioning

confidence: 99%

Section: General Procedures For the Reactions Of Endocyclic Enaminonesmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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[2+2] Cycloadditions of electron-poor acetylenes to endocyclic enaminones: ring-expansion reactions

et al. 2015

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“…[25][26][27] Recently, polysubstituted butadienes have been prepared by microwave-assisted [2þ2] cycloadditions of enaminones to electron-poor acetylenes. [28,29] Polysubstituted aminobutadienes prepared by this procedure are suitable for the preparation of polysubstituted pyridine derivatives. They also represent a group of isomeric intermediates in regard to the aminobutadienes prepared via the Michael addition in Bohlmann-Rahtz synthesis of pyridine derivatives.…”

Section: Introductionmentioning

confidence: 99%

Reactions of Methyl Ketones and (Hetero)arylcarboxamides with N,N-Dimethylacetamide Dimethyl Acetal. A Simple Metal-Free Synthesis of 2,4,6-Trisubstituted Pyridines

et al. 2015

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Two metal-free syntheses of 2,4,6-trisubstituted pyridines 10a-m and 16a-j are described. N, N, pyridin-2-amines 10 were prepared from aryl or heteroaryl methyl ketones which were transformed with N,Ndimethylacetamide dimethyl acetal (DMADMA) into enaminones 4a-m, followed by treatment with ammonium acetate to give (Z)-3-amino-1-(substituted)but-2-en-1-ones 5a-m. These were treated with DMADMA under microwave irradiation in a closed vessel at 1308C, to give via intermediates 7-9 the final products 10a-m. N 2 ,N 2 ,N 4 ,N 4 -Tetramethyl-6-(substituted) pyridine-2,4-diamines 16a-j were prepared in a one-pot synthesis from the corresponding carboxamides 11a-j by treatment with an excess of DMADMA in a closed vessel under microwave irradiation to give via intermediates 12a-j to 15a-j the final products 16a-j. X-Ray single crystal diffractometry studies of the enaminones 5c, 5g, 5i, 5j, and 5m and 2,4,6-trisubstituted pyridines 16a, 16b, 16g, 16i, and 16j were consistent with the expected structures.

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“…[15,16] A number of domino reactions have been developed by using this kind of in situ generated β-enamino esters to react further with other nucleophilic or electrophilic reagents to give versatile nitrogen-containing compounds and N,O-heterocycles. [17][18][19][20][21][22][23] We have also developed several domino reactions of the in situ formed β-enamino esters with nitrostyrene, [24] indole, [25] aromatic aldehydes, [26,27] α,β-unsaturated aldehydes, [28] arylidene malononitrile [29] and dicarbonyl compounds. [30,31] As a continuation of our approach toward the design of new domino synthetic procedures involving the use of β-enaminones and β-enamino esters as the key components, in this text we wish to report the one-pot sequential reactions of arylamines, methyl propiolate and 3-nitrochromenes for the efficient and diastereoselective synthesis of 3-(3-nitro-2-phenylchroman-4-yl)-3-arylaminoacrylates.…”

Section: Introductionmentioning

confidence: 99%

One‐pot Sequential Reaction for the Synthesis of Polysubstituted 3‐(3‐Nitro‐2‐phenylchroman‐4‐yl)‐3‐arylaminoacrylates

2013

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The one-pot sequential reaction of arylamines, methyl propiolate and 2-aryl-3-nitrochromenes without any catalyst in refluxing ethanol afforded the polysubstituted 3-(3-nitro-2-phenylchroman-4-yl)-3-arylaminoacrylates in good yields and with high diastereoselectivity. Reaction mechanism was believed involving the initial formation of β-enamino ester and sequential Michael addition. Experimental Reagents and apparatusAll reactions were monitored by TLC. Melting points were taken on a hot-plate microscope apparatus. IR spectra were obtained on a Bruker Tensor 27 spectrometer (KBr disc). 1 H and 13 C NMR spectra were recorded with a Bruker AV-600 spectrometer with DMSO-d 6 as solvent and TMS as internal standard (600 and 150 MHz for 1 H and 13 C NMR spectra, respectively). HPLC/MS were measured at Bruker MicroTOF spectrometer. Arylamines, methyl propiolates and other reagents are commercial reagents and used as received. 2-Aryl-3-nitrochromenes were prepared according to the published methods. Solvents were purified by standard techniques. General procedure for the one-pot reactions of arylamines, methyl propiolate and 3-nitrochromenesA mixture of arylamine (2.0 mmol) and methyl propiolate (2.0 mmol, 0.168 g) in 5.0 mL ethanol was stirred at room temperature for 24 h. Then 2-aryl-3-nitrochromene (2.0 mmol) was added and the solution was heated to gentle reflux for additional 6 h. After cooling, the resulting precipitates were collected by filtration and washed with little cold ethanol to give the pure product for analysis.(Z)-Methyl 3-(6-chloro-3-nitro-2-phenylchroman-4yl)-3-(4-methoxyphenylamino)acrylate (1a): white solid, 89%, m.p. 140 -142 ℃ ; 1 H NMR (600 MHz, DMSO-d 6 ) δ: 9.95 (d, J＝13.2 Hz, 1H, NH), 7.46 (d, J＝7.2 Hz, 2H, ArH), 7.41 (t, J＝7.2 Hz, 2H, ArH), 7.38-7.35 (m, 1H, ArH), 7.32-7.30 (m, 2H, ArH), Synthesis of Polysubstituted 3-(3-Nitro-2-phenylchroman-4-yl)-3-arylaminoacrylates Chin.

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[2+2] Cycloaddition of electron-poor acetylenes to (E)-3-dimethylamino-1-heteroaryl-prop-2-en-1-ones: synthesis of highly functionalized 1-heteroaroyl-1,3-butadienes

Cited by 39 publications

References 33 publications

[2+2] Cycloadditions of electron-poor acetylenes to endocyclic enaminones: ring-expansion reactions

[2+2] Cycloadditions of electron-poor acetylenes to endocyclic enaminones: ring-expansion reactions

Reactions of Methyl Ketones and (Hetero)arylcarboxamides with N,N-Dimethylacetamide Dimethyl Acetal. A Simple Metal-Free Synthesis of 2,4,6-Trisubstituted Pyridines

One‐pot Sequential Reaction for the Synthesis of Polysubstituted 3‐(3‐Nitro‐2‐phenylchroman‐4‐yl)‐3‐arylaminoacrylates

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