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19544393521
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Manuscript in preparation
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Manuscript in preparation.
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[9a] Amnesia-reversal: D. E. Butler, J. D. Leonard, B. W. Caprathe, Y. J. L'Italien, M. R. Pavia, F. M. Hershenson, P. H. Poschel, J. G. Marriott, J. Med. Chem. 1987, 30, 498-503.
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[10c] R. J. Nash, L. E. Fellows, J. V. Dring, G. W. J. Fleet, A. Girdhar, N. G. Ramsden, J. M. Peach, M. P. Hegarty, A. M. Schofield, Phytochemistry 1990, 29, 111 and references therein.
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19544379846
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note
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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.
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22
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19544371721
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note
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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.
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23
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19544378482
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note
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For a detailed study of the reaction between vinyl ether 1 and β-nitrostyrene and subsequent β-lactam formation, see ref. [5].
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24
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19544375029
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note
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1H NMR analysis of the crude reaction mixtures and integration of the corresponding proton signals; see Experimental Section.
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25
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19544376630
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note
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Increasing the pressure from 12 to 15 kbar merely resulted in polymerisation of the starting compound 2a.
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26
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19544372935
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note
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1H NMR analysis of the crude reaction mixtures; 95% at 8 kbar, 50% at 6 kbar and 20% at 4 kbar.
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27
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84885451493
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The reaction of nitronates as dipoles in [3 + 2] cycloadditions was first discovered by: V.A. Tartakovskii, I. E. Chlenov, S. S. Smagin, S. S. Noviov, Izv. Akad. Nauk. SSSR, Ser. Khim. 1964, 583-584;
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Tartakovskii, V.A.1
Chlenov, I.E.2
Smagin, S.S.3
Noviov, S.S.4
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29
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0004115272
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(Ed. H. Feuer), VCH Publishers, Inc., New York
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also described by K. B. G. Torssell, in: Nitrile oxides, Nitrones and Nitronates in Organic Synthesis (Ed. H. Feuer), VCH Publishers, Inc., New York, 1988.
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(1988)
Nitrile Oxides, Nitrones and Nitronates in Organic Synthesis
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Torssell, K.B.G.1
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30
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19544367088
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note
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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.
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31
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19544387397
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note
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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.
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33
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0004045862
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New York, Reinhold Publishing Corporation, Chapman & Hall, Ltd, London
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See e.g. Fieser & Fieser, Advanced Organic Chemistry, p. 673, 1961. New York, Reinhold Publishing Corporation, Chapman & Hall, Ltd, London.
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Advanced Organic Chemistry
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34
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19544388917
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note
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1H NMR analysis of the crude reaction mixture showed 75% conversion of enol ether 1.
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35
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0040164411
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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.
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Klärner, F.-G.1
Breitkopf, V.2
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36
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19544382859
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note
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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:
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[25a] M. J. Kamlet, J.-L. M. Abboud, M. H. Abraham, R. W. Taft, J. Org. Chem. 1983, 48, 2877.
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Kamlet, M.J.1
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Taft, R.W.4
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38
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0004018410
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VCH, Weinheim, Germany
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[25b] Christian Reichardt, Solvents and Solvent Effects in Organic Chemistry, 2nd ed., 1990, VCH, Weinheim, Germany.
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Reichardt, C.1
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0026052599
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[25c] Freezjng pressures, see for example references cited in: N. S. Isaacs, Tetrahedron 1991, 47, 8463-8497.
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Isaacs, N.S.1
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S. Matysiak, H.-P. Fitznar, R. Schnell, W. Pfleiderer, Helv. Chim. Acta 1998, 81, 1545-1566.
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42
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0006293976
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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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Dornow, A.1
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A. S. Polyanskaya, V. V. Perekalin, N. I. Aboskalova, Z. I. Demireva, L. N. Sokolova, Z. A. Adulkina, J. Org. Chem. USSR (Engl. Transl.) 1979, 15, 1859-1862.
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