Thermal and catalytic intramolecular [4+2]-cycloaddition in 2-alkenylfurans

Zubkov, Fedor I.; Nikitina, Eugeniya V.; Varlamov, A. V.

doi:10.1070/rc2005v074n07abeh001180

Cited by 49 publications

(31 citation statements)

References 22 publications

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“…The most low-field chemical shifts of C-2 (d 208À211 ppm) and C-6 (d 170À176 ppm) carbon atoms, together with well-identified C-10a and C-8 (d 79À91 ppm) carbon atom signals are the most characteristic in 13 C NMR spectra of cycloaddition products 2À5, 7,8.…”

Section: Resultsmentioning

confidence: 97%

“…The usual work-up gives a mixture of products, from which the target piperidones 6 can be separated easily (although with low yield) as hydrochlorides (see Experimental section). 2-Furylpiperidones 6a-c react smoothly with acryloyl chloride and maleic anhydride in boiling toluene, giving exo-products of cycloaddition-2H-8,10a-epoxypirido[2,1-a]isoindoles (8) and their 7-carboxylic acids (7)-with moderate yields.…”

Section: Resultsmentioning

confidence: 98%

“…To achieve the aforementioned goal, we used an intramolecular variant of the Diels-Alder reaction in the piperidone series (IMDAF), containing the unsaturated moiety [8][9][10]. We have used the same strategy before for various preparations of heterocyclics -particularly for isoindolo [2,1-a]quinolines [11], isoindolo [2,1-b][2]benzazepines [12], and isoindolo[1,2-a]isoquinolines [13], with the structure close to natural alkaloids.…”

Section: Introductionmentioning

confidence: 99%

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[4+2] Cycloaddition of α,β‐unsaturated acid anhydrides to 2‐furylpiperidin‐4‐ones: The short route to annulated 8,10a‐epoxypyrido[2,1‐a]isoindoles

Zubkov

Airiyan

Dzyubenko

et al. 2010

Journal of Heterocyclic Chem

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Scheme 3. Cycloaddition with unsymmetrical substituted piperidones 1a,c.Scheme 2. Cycloaddition with symmetrical substituted piperidones 1b,d. 402Vol 47 F.I. Zubkov, I.K. Airiyan, A.A. Dzyubenko, N.I. Yudina, V.P. Zaytsev, E.V. Nikitina, A.V. Varlamov, V.N. Khrustalev, D.G. Grudinin Journal of Heterocyclic Chemistry DOI 10.1002/jhet 79À91 ppm) carbon atom signals are the most characteristic in 13 C NMR spectra of cycloaddition products 2À5, 7, 8.A large number of methods for pentacyclic indolizinoindole core synthesis are known [16], and the similarity of this heterocyclic system to some alkaloids encourages further research. Several short studies [17] dedicated to the synthesis of benzo [1,2]indolizino [8,7-b]indol-4-carboxylic acids of type 10 from maleic anhydride and N-furfurylidene(indol-3-yl)ethanamines have been published recently. An elegant reaction sequence (acylation/ Pictet-Spengler/ IMDAF) proceeds in mild conditions (Scheme 7). To build some alkaloid-like polycyclic structures by Suzuki coupling, we needed to synthesize 3-halosubstituted adducts 10.As was shown earlier [17], the condensation of N-furfurylidenetriptamines 9a,b with maleic anhydride proceeds stereoselectively, yielding the single exo-diastereoisomer 10a,b. Analogous interaction of azomethine 9c with citraconic anhydride leads with good yield to the mixture of polycycles 12A and 12B (in approximatively equal amounts), isomeric by methyl group position, that we could not separate by recrystallization.Haloderivatives 10a,b are white powders, low soluble even in DMSO, so to determinate their structure by 1 H and 13 C NMR we have synthesized esters 11. The spatial structure of these latter was established by NOE spectra, in which we can observe a significant change of H-13b proton integral intensity, while irradiating H-4a (and vice versa). This fact indicated the spatial closeness (cis-orientation) of the above protons.In the last part of our work we have applied an analogous method for the synthesis of spinacines annelated with epoxyisoindole moiety. The condensation of histamine with aromatic aldehydes in an alkaline medium leading to spinacines (Fig. 1) Acylation of spinacines 13 with maleic anhydride at room temperature occurs exclusively on the N-5 nitrogen atom of the tetrahydropyridine ring -products of anhydride addition to imidazole cycle were not found in the reaction mixture. Acylation (same as in previous cases) is accompanied by simultaneous [4þ2] cycloaddition giving exo-adducts 14. We suppose the cis-position of H-7a and H-11b protons by analogy with adducts 2-4, 7, 8, and 10. Cycloaddition products are extremely hard-soluble and hard-crystallizing tawny powders. The low-field singlet signal of H-2 proton at d $7.5 ppm and broaded one of H-11b at d $5.3 ppm, as well as associated exo-protons H-7a, H-8 with 3 J 7a,8 ¼ 8.9À9.1 Hz (at d 2.5À3.0 ppm), can be considered as characteristic. In the carbon spectrum, C-2 and C-11a peaks at d 135À136 and 90À91 ppm, respectively, are remarkable. EXPERIMENTALAll reagents were ...

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Section: Resultsmentioning

confidence: 97%

Section: Resultsmentioning

confidence: 98%

Section: Introductionmentioning

confidence: 99%

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[4+2] Cycloaddition of α,β‐unsaturated acid anhydrides to 2‐furylpiperidin‐4‐ones: The short route to annulated 8,10a‐epoxypyrido[2,1‐a]isoindoles

Zubkov

Airiyan

Dzyubenko

et al. 2010

Journal of Heterocyclic Chem

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“…The presence of a secondary nitrogen atom opens a broad range of possibilities for modifying such isoindoles at the amide group. Previous attempts to synthesize such compounds by the cycloaddition of maleic anhydride to furfurylamine in various solvents proved unsuccessful [22]. Only acid 2e was obtained in 17% yield upon heating at reflux in water for 5 h with an equimolar amount of maleic anhydride.…”

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confidence: 99%

Cycloaddition of furfurylamines to maleic anhydride and its substituted derivatives

Zaytsev

Mikhailova

Airiyan

et al. 2012

Chem Heterocycl Comp

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Functionally substituted epoxyisoindolones hold interest for use in organic synthesis. Pseudo-sugars annelated with azaheterocycles [1][2][3], and various condensed heterocyclic compounds containing an isoindole fragment may be obtained on the basis of these compounds [4][5][6][7][8][9][10]. A recently developed method for the synthesis of isoindol-1-ones holds considerable promise in this regard. This method is based on the acylation of N-aryl-or N-alkylfurfurylamines by unsaturated acid derivatives with subsequent intramolecular [4+2] cycloaddition of the resultant unsaturated amides [11][12][13][14][15][16][17][18][19].The development of this approach is an elaboration of the two-step preparative method for the synthesis of 7-carboxy-2-R-isoindol-1-ones [20] based on [4+2] cycloaddition of maleic anhydride to N-substituted furfurylamines. We studied the scope of this reaction and showed the effect of the substituent at the furfurylamine nitrogen atom on the cycloaddition. Conditions were found for the aromatization of the oxabicycloheptene fragment to give 7-carboxyphthalimidines [21].In the present work, we have studied the regio-and stereoselectivity of the cycloaddition of maleic, citraconic, dibromomaleic, and dichloromaleic anhydrides to difurfurylamines as well as to phenyl-and benzylfurfurylamines. An attempt was made to evaluate the effect of substituents in the oxabicycloheptene fragment on the capacity of the Diels-Alder adducts to undergo aromatization.Starting furfurylamines 1a-h were obtained as light, mobile oils by the reduction of the corresponding Schiff bases using sodium borohydride in ethanol.

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“…[24] Similarly, only (3 + 2)-cycloadducts were obtained by other authors in reactions of diverse D-A cyclopropanes with a variety of 1,3-dienes. [25] Furans themselves are often used as 4p-component in both Diels-Alder reactions [26] and (4 + 3)-cycloadditions with various 1,3-dipoles. [27] However, furan derivatives can also react as 2p-components affording products of (2 + 1)-, [3,28] (2 + 2)-, [29] (2 + 3)- [30] and (2 + 4)-cycloadditions.…”

Section: (3 + 2)-cycloaddition To 13-dienesmentioning

confidence: 99%

Donor‐Acceptor Cyclopropanes in the Synthesis of Carbocycles

Ivanova

Trushkov

2019

The Chemical Record

109

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Donor‐acceptor cyclopropanes not only participate in a broad range of ring openings with nucleophiles, electrophiles, radical and red‐ox agents, but also are excellent substrates for various (3+n)‐cycloaddition and (3+n)‐annulation processes. Moreover, under treatment with Lewis acid donor‐acceptor cyclopropanes can produce new ring systems via isomerization or cyclodimerization. Authors’ contribution to the synthesis of diverse carbocycles from donor‐acceptor cyclopropanes is summarized in this account.

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Thermal and catalytic intramolecular [4+2]-cycloaddition in 2-alkenylfurans

Cited by 49 publications

References 22 publications

[4+2] Cycloaddition of α,β‐unsaturated acid anhydrides to 2‐furylpiperidin‐4‐ones: The short route to annulated 8,10a‐epoxypyrido[2,1‐a]isoindoles

[4+2] Cycloaddition of α,β‐unsaturated acid anhydrides to 2‐furylpiperidin‐4‐ones: The short route to annulated 8,10a‐epoxypyrido[2,1‐a]isoindoles

Cycloaddition of furfurylamines to maleic anhydride and its substituted derivatives

Donor‐Acceptor Cyclopropanes in the Synthesis of Carbocycles

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