Long-range correlations ( n j C,H n &gt; 3 ) in the HMBC spectra of 3-(4-oxo-4H-chromen-3-YL)-acrylic acid ethyl esters

Araya‐Maturana, Ramiro; Gavín-Sazatornil, José A.; Heredia-Moya, Jorge; Pessoa‐Mahana, Hernán; Weiss-López, Boris

doi:10.1590/s0103-50532005000400028

Cited by 10 publications

(11 citation statements)

References 20 publications

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“…The E/Z product mixture has a 55/40 E/Z ratio and an overall yield of 95% [16]. When N-vinylpyrrolidinone, a dienophile already used in inverse electron demand Diels-Alder reactions [17], reacted with 1 in toluene at 140 • C in a sealed tube, a mixture of isomeric tetracyclic compounds 5 and 6, along with the xanthone 2, were obtained in yields of 35%, 15% and 2%, respectively (Scheme 2).…”

Section: Resultsmentioning

confidence: 99%

Ethyl (1R,10S,12R,15S)-4-Hydroxy-2-oxo-15- (2-oxo-1-pyrrolidinyl)-9-oxatetracyclo[10.2.2.01,10.03,8]hexadeca-3,5,7,13-tetraene-13-carboxylate

Heredia-Moya

Araya‐Maturana

2017

Molbank

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N-Vinylpirrolidinone reacts with (E)-ethyl 5-hydroxy-3-(4-oxo-4H-chromen-3-yl) acrylate (1) through a domino reaction similar to that reported reaction for ethyl vinyl ether. Inverse electron demand Diels-Alder (IEDDA)-elimination-IEDDA generates isomeric tetracycles 5 and 6. The assignment of the relative stereochemistry of the products was made by comparing the proton couplings with those obtained by reaction with ethyl vinyl ether.

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Section: Resultsmentioning

confidence: 99%

Ethyl (1R,10S,12R,15S)-4-Hydroxy-2-oxo-15- (2-oxo-1-pyrrolidinyl)-9-oxatetracyclo[10.2.2.01,10.03,8]hexadeca-3,5,7,13-tetraene-13-carboxylate

Heredia-Moya

Araya‐Maturana

2017

Molbank

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“…The starting chromones 3, 11-13 were obtained by Wittig reactions of parent 3-formylchromone (7) and its 5-hydroxy-derivative (8) with carboethoxymethylenetriphenylphosphorane (9) or triphenylphosphoranylidenacetonitrile (10). The E/Z product mixtures were obtained with good overall yields and variable E/Z ratios (Table 1).…”

Section: Resultsmentioning

confidence: 99%

“…Oxo-4H-chromen-3-yl)acrylic acid ethyl ester (E-3) 10. Yield 50 %, crystallized from EtOAc/hexane as colorless needles.…”

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confidence: 99%

Domino Inverse Electron Demand Diels-Alder Reactions of Chromones with Ethyl Vinyl Ether

Araya‐Maturana¹,

Heredia-Moya²,

Krohn³

et al. 2007

HETEROCYCLES

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E)-Ethyl 3-(4-oxo-4H-chromen-3-yl)acrylate (3), (E)-3-(4-oxo-4Hchromen-3-yl)-2-propenenitrile (12) and their 5-hydroxy-derivatives 11 and 13 undergo alternative, solvent dependent, domino reactions with ethyl vinyl ether. Inverse electron demand Diels-Alder (IEDDA)-elimination-IEDDA generates isomeric tetracycles 15a-d and 16a-d. Instead, IEDDA-elimination-intramolecular elimination reactions provides xanthone 17 or 2-hydroxybenzophenones 18a-d, respectively. In non-polar solvents propenenitriles 12 and 13 experience a third alternative domino sequence: IEDDA-elimination-ene reaction, yielding the highly functionalized tricyclic compounds 21 and 22. 7 9 E-3 50 Z-3 49 8 9 E-11 55 Z-11 40 7 10 E-12 13 Z-12 63 8 10 E-13 30 Z-13 60 * Conditions: toluene, reflux, 2 hSurprisingly, when chromone E-11 was allowed to react with ethyl vinyl ether (14), in a sealed tube at 140 ºC in toluene for 3 days, tetracyclic compounds 15a and 16a were obtained in 56% yield and a 84:16 (15a:16a) ratio along with 5% of xanthone 17 instead of the expected benzophenone 18a (Scheme 2). Scheme 3. Plausible mechanism of the domino reaction of E-11 with vinyl ethyl ether (14). A strong solvent effect directs these alternative reaction paths. Thus, when ethyl vinyl ether, methanol or acetone was used as solvent at 80 °C, only the tetracycles 15a and 16a (path A) and benzophenone 18a (path C) were obtained in variable yields. The xanthone 17 was not detected (path B). In toluene, at the same conditions, compounds 15-17 (path A and B) were obtained in very low yield.15 16 18 E-3 80 3 38 19 11 31 E-12 80 3 10 4 53 22 E-13 80 3 26 --44 4 A comparison between the reactions of chromone E-3 and the 5-hydroxy-derivative E-11 showed that the presence of the hydroxyl group at C-5 causes an increase in the reactivity toward dienophile 14. The amount of unreacted E-3 was about twice as much as unreacted E-11, both recovered under similar reaction conditions. This evidences that the electron withdrawing effect of the intramolecular hydrogen bonding in E-11 increases the reactivity of the diene moiety. When the ethoxycarbonyl substituent was replaced by a cyano group (compounds E-12 and E-13), a J = 7.1 Hz, CO 2 CH 2 J 2 = 7.0 Hz, CH(OCHHCH 3 )CH 3 ), 3.46 (dq, 1H, J 1 = 8.9 Hz, J 2 = 7.0 Hz, CH(OCHHCH 3 )CH 3 ), 3.70 (dd, 1H, J 1 = 9.0 Hz, J 2 = 7.1 Hz, OCHHCH 3 ), 3.74 (dd, 1H, J 1 = 9.0 Hz, J 2 = 7.1 Hz, OCHHCH 3 ), 3.94 (q, 1H, J = 6.4 Hz, CH(OEt)CH 3 ), 4.22 (ddd, 1H, J 1 = 9.0 Hz, J 2 = 7.5 Hz, J 3 = 1.4 Hz, H3), 4.29 (dd, 1H, J 1 = 13.5 Hz, J 2 = 3.8 Hz, H4a), 6.42 (dd, 1H, J 1 = 8.3 Hz, J 2 = 0.8 Hz, H5), 6.54 (dd, 1H, J 1 = 8.3 Hz, J 2 = 0.8 Hz, H7), 7.04 (d, 1H, J = 1.3 Hz, H1), 7.35 (dd, 1H, J 1 = J 2 = 8.3 Hz, H6), 11.37 (s, 1H, OH); 13 C-NMR δ (CDCl 3 ) 14.8 (CH(OCH 2 CH 3 )CH 3 ), 15.3 (OCH 2 CH 3 ), 17.6 (CH(OEt)CH 3 ), 30.7 (C-4), 53.7 (C-9a), 65.8 (CH(OCH 2 CH 3 )CH 3 ), 66.1 (OCH 2

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“…1 H NMR (300 MHz, CDCl 3 ): 7.52 (ddd, 1H, J 1 = 7.9 Hz, J 2 = 7.2 Hz, J 3 = 1.1 Hz, 6-H), 7.56 (dd, 1H, J 1 = 8.5 Hz, J 2 = 1.1 Hz, 8-H), 7.77 (ddd, 1H, J 1 = 8.5 Hz, J 2 = 7.2 Hz, J 3 = 1.7 Hz, 7-H), 8.32 (dd, 1H, J 1 = 7.9 Hz, J 2 = 1.7 Hz, 5-H), 8.57 (s, 1H, 2-H), 10.40 (s, 1H, CHO). 3-(4-oxo-4H-chromen-3-yl)acrylate (4) [16,17] MP: 111.5-112.5ºC.…”

Section: -Formyl-4[h]-1-benzopyran-4-one (1) [8]mentioning

confidence: 99%

“…Generally, the IC 50 for oxygen uptake inhibition is about one order of magnitude greater than the IC 50 for cytotoxicity. In relation to these compounds, spectroscopic and reactivity studies of chromone 4 have also been reported [16,17].…”

Section: No 4 519 -524mentioning

confidence: 99%

Effects of Simple and Angular Chromones on Tumor Cell Respiration

Araya‐Maturana

Heredia-Moya

Donoso‐Tauda

et al. 2008

Natural Product Communications

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A set of structurally related compounds incorporating a chromone moiety as an essential component of their structures were tested against the TA3 mouse carcinoma cell line and its multidrug-resistant variant TA3-MTX-R. A tentative structureactivity relationship was found for this family of substances, suggesting that a Michael addition at C-1 is involved in the mechanism that provokes the activities.

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Long-range correlations ( n j C,H n > 3 ) in the HMBC spectra of 3-(4-oxo-4H-chromen-3-YL)-acrylic acid ethyl esters

Cited by 10 publications

References 20 publications

Ethyl (1R,10S,12R,15S)-4-Hydroxy-2-oxo-15- (2-oxo-1-pyrrolidinyl)-9-oxatetracyclo[10.2.2.01,10.03,8]hexadeca-3,5,7,13-tetraene-13-carboxylate

Ethyl (1R,10S,12R,15S)-4-Hydroxy-2-oxo-15- (2-oxo-1-pyrrolidinyl)-9-oxatetracyclo[10.2.2.01,10.03,8]hexadeca-3,5,7,13-tetraene-13-carboxylate

Domino Inverse Electron Demand Diels-Alder Reactions of Chromones with Ethyl Vinyl Ether

Effects of Simple and Angular Chromones on Tumor Cell Respiration

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Long-range correlations ( n j C,H n > 3 ) in the HMBC spectra of 3-(4-oxo-4H-chromen-3-YL)-acrylic acid ethyl esters

Cited by 10 publications

References 20 publications

Ethyl (1R*,10S*,12R*,15S*)-4-Hydroxy-2-oxo-15- (2-oxo-1-pyrrolidinyl)-9-oxatetracyclo[10.2.2.01,10.03,8]hexadeca-3,5,7,13-tetraene-13-carboxylate

Ethyl (1R*,10S*,12R*,15S*)-4-Hydroxy-2-oxo-15- (2-oxo-1-pyrrolidinyl)-9-oxatetracyclo[10.2.2.01,10.03,8]hexadeca-3,5,7,13-tetraene-13-carboxylate

Domino Inverse Electron Demand Diels-Alder Reactions of Chromones with Ethyl Vinyl Ether

Effects of Simple and Angular Chromones on Tumor Cell Respiration

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Ethyl (1R,10S,12R,15S)-4-Hydroxy-2-oxo-15- (2-oxo-1-pyrrolidinyl)-9-oxatetracyclo[10.2.2.01,10.03,8]hexadeca-3,5,7,13-tetraene-13-carboxylate

Ethyl (1R,10S,12R,15S)-4-Hydroxy-2-oxo-15- (2-oxo-1-pyrrolidinyl)-9-oxatetracyclo[10.2.2.01,10.03,8]hexadeca-3,5,7,13-tetraene-13-carboxylate