Complete and remarkable reversal of chemoselectivity in [4 + 2] cycloadditions involving electron-poor indoles as dienophiles. Diels-Alder versus hetero-Diels-Alder processes

Journal of Organic Chemistry

Volumn 68, Issue 21, 2003, Pages 7990-8002

  Chrétien, Antony ^a   Chataigner, Isabelle ^a   L'Hélias, Nathalie ^a   Piettre, Serge R ^a  

^a UNIVERSITÉ DE ROUEN   (France)

Author keywords

[No Author keywords available]

Indexed keywords

THERMAL ACTIVATION;

ADDITION REACTIONS; CHEMICAL BONDS; HYDROLYSIS; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; SUBSTITUTION REACTIONS; X RAY DIFFRACTION ANALYSIS;

ALDEHYDES;

2 [2,3 DIMETHYL 9 (TOLUENE 4 SULFONYL) 1,4,9,9A TETRAHYDROCARBAZOL 4A YL] 2,3 DIHYDROPYRAN 4 ONE; 2 [2,3 DIMETHYL 9 (TOLUENE 4 SULFONYL) 1,4,9,9A TETRAHYDROCARBAZOL 4A YL] 4,5 DIMETHYL 3,6 DIHYDRO 2H PYRAN 2 CARBOXYLIC ACID; 2,3 DIMETHYLBUTADIENE; 3 INDOLECARBALDEHYDE; 4A (4,5 DIMETHYL 3,6 DIHYDRO 2H PYRAN 2 YL) 2,3 DIMETHYL 9 (TOLUENE 4 SULFONYL) 4,4A,9,9A TETRAHYDRO 1H CARBAZOLE; 5 HYDROXY 1 METHOXY 5 [1 (TOLUENE 4 SULFONYL) 1H INDOL 3 YL]PENT 1 EN 3 ONE; ALDEHYDE DERIVATIVE; ALKADIENE; CARBON; CYCLOHEXANONE; CYCLOHEXENE DERIVATIVE; INDOLE 3 GLYOXALATE; INDOLE DERIVATIVE; METHANOL; SILANE DERIVATIVE; UNCLASSIFIED DRUG; ZINC CHLORIDE;

ARTICLE; CATALYSIS; CHEMICAL BOND; CHEMICAL INTERACTION; CHEMICAL REACTION; CHEMICAL STRUCTURE; CONFORMATION; CYCLOADDITION; DIELS ALDER REACTION; ELECTRON; HYDROLYSIS; PROTON NUCLEAR MAGNETIC RESONANCE; STRUCTURE ANALYSIS; X RAY DIFFRACTION;

EID: 1842513529     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo034719b     Document Type: Article

References (60)

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37. The relative rates of both cycloaddition and polymerisation processes involved here can be unequally influenced by various factors among which the quality of the Lewis acid catalyst, or of the solvent, for example. The overall result can thus vary somewhat, depending on the experiment and lead to differences in reproducibility of yields and ratios. Nevertheless, the general trends observed in these experiments are reproducible.
38. The use of pressure alone has the disadvantage of producing a large amount of polymers. Thus, while a complete conversion is observed and cycloadduct 10 is formed in an exclusive manner at 50 °C, the reaction is of little practical use (entry 11). Despite many efforts, these conditions could not been translated into good isolated yields.
39. EuFOD is europium tris(6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedionate).
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47. To the best of our knowledge, the only reported case of a ketoamide undergoing a [4 + 2] heterocycloaddition involves unsaturated 3-oxopyrrolidinone of the type 31 and Danishefsky diene 2c, when either heated at 130 °C or compressed at 10 kbar. Compound 31 delivered either normal Diels-Alder cycloadducts 32 and heterocycloadducts 33 in variable amounts or exclusively the same cycloadducts 33, depending on the conditions and the substituents. See: (a) Tsuda, Y.; Hosoi, S.; Katagiri, N.; Kaneko, C.; Sano, T. Heterocycles 1992, 33, 497-502.
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50. Inasmuch as the heterocycloaddition suppresses the electron-withdrawing group on the indole ring, the normal [4 + 2] cycloaddition must occur prior to the hetero Diels-Alder reaction in the process leading to bisadducts of the type 7 (29 and 30).
51. H4-H3 = 3.4, 7.9 Hz.
52. Analysis of the unseparable, purified mixture revealed the presence of two major compounds, whose relative stereochemistry could not be ascertained.
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60. 13C NMR signals is reported.