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Volumn , Issue 3, 2001, Pages 553-560

Novel five/five- and six/five-membered bicyclic nitroso acetals from high-pressure-promoted cyclisation reactions of p-methoxybenzyl vinyl ether, 1-nitro-2-heteroaryl ethenes, and mono- and di-substituted olefins

Author keywords

Alkenes; Cycloadditions; Heterocycles; High pressure chemistry; Nitroso acetals

Indexed keywords

1 METHOXY 4 [(VINYLOXY)METHYL]BENZENE; 3 [2 NITROETH 1 ENYL]PYRIDINE; ACRYLIC ACID METHYL ESTER; ALKENE DERIVATIVE; BENZENE DERIVATIVE; BENZYL DERIVATIVE; BICYCLO COMPOUND; ETHYLENE; NITRO DERIVATIVE; NITROSO DERIVATIVE; PYRIDINE DERIVATIVE; UNCLASSIFIED DRUG; VINYL DERIVATIVE;

EID: 0035142866     PISSN: 1434193X     EISSN: None     Source Type: Journal    
DOI: 10.1002/1099-0690(200102)2001:3<553::AID-EJOC553>3.0.CO;2-N     Document Type: Article
Times cited : (44)

References (49)
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    • Manuscript in preparation
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  • 21
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    • note
    • The configuration of the diastereomers formed was assigned based on 2D-NOESY NMR studies of the main diastereomers. The main diastereomers of 4a and 4b were elucidated as resulting from an endo [4 + 2], anti (with respect to the aryl group) and an exo [3 + 2] approach. The relative configuration of the minor diastereomer of 4c resulted from an endo [4 + 2], anti (with respect to the aryl group) and an endo [3 + 2] approach.
  • 22
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    • note
    • The anti-attack of the bulky N-phenyl maleimide dipolarophile is probably due to the steric hindrance of the pyridyl- and p-methoxybenzyl-substituents which shield one side of the nitronate, whereas the endo-selectivity might arise from secondary orbital overlap between the N-phenyl-substituent and the nitronate dipole.
  • 23
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    • note
    • For a detailed study of the reaction between vinyl ether 1 and β-nitrostyrene and subsequent β-lactam formation, see ref. [5].
  • 24
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    • note
    • 1H NMR analysis of the crude reaction mixtures and integration of the corresponding proton signals; see Experimental Section.
  • 25
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    • note
    • Increasing the pressure from 12 to 15 kbar merely resulted in polymerisation of the starting compound 2a.
  • 26
    • 19544372935 scopus 로고    scopus 로고
    • note
    • 1H NMR analysis of the crude reaction mixtures; 95% at 8 kbar, 50% at 6 kbar and 20% at 4 kbar.
  • 30
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    • note
    • Assignment was based on 2D-NOESY NMR studies of the main diastereomers of 10 (80%), 11 (70%) and 12 (47%). The diastereomer of compound 11 formed in 30% and the diastereomer of compound 12 formed in 40% yield have been assigned on the basis of an endo,anti approach to the C(2) alkoxy substituent.
  • 31
    • 19544387397 scopus 로고    scopus 로고
    • note
    • α-Nitro attack results in formation of a six-membered cyclic nitronate and β-nitro attack results in formation of the five-membered cyclic nitronate.
  • 33
    • 0004045862 scopus 로고
    • New York, Reinhold Publishing Corporation, Chapman & Hall, Ltd, London
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  • 34
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    • note
    • 1H NMR analysis of the crude reaction mixture showed 75% conversion of enol ether 1.
  • 35
    • 0040164411 scopus 로고    scopus 로고
    • The reversibility of the Diels-Alder reaction under high-pressure conditions has been described in the literature. See for example: F-G. Klärner, V. Breitkopf, Eur. J. Org. Chem. 1999, 2757-2762 and references therein.
    • (1999) Eur. J. Org. Chem. , pp. 2757-2762
    • Klärner, F.-G.1    Breitkopf, V.2
  • 36
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    • note
    • 3 (0.00) < THF (0.55), acetone (0.48)]. The more basic solvents tetrahydrofuran and acetone might shield the β-position of the polarised nitroalkene more effectively and consequently nucleophilic attack at the α-position of the nitroalkene might be favoured. Thus the difference in solvent basicity might result in a different degree of shielding of the β-position of the nitroalkene. See:
  • 39
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    • [25c] Freezjng pressures, see for example references cited in: N. S. Isaacs, Tetrahedron 1991, 47, 8463-8497.
    • (1991) Tetrahedron , vol.47 , pp. 8463-8497
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  • 42
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    • A. Dornow, B. Boberg, Justus Liebigs Ann. Chem. 1952, 101-111. We were not able to repeat the described method. The nitro alcohol was the only product isolated.
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  • 49
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    • Springer Verlag: New York
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