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70350039937
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See references [6g] and [6i] for specific examples of pyridine ring formation from 2-en-4-yn-1-imines.
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See references [6g] and [6i] for specific examples of pyridine ring formation from 2-en-4-yn-1-imines.
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Such reactions are also called reverse Cope cyclizations/eliminations. For a review: N. J. Cooper, D W Knight, Tetrahedron 2004, 60, 243.
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Alkynes: a) S. K. Pradharan, K. G. Akamanchi, P. P. Divakaran, P. M. Pradhan, Heterocycles 1989, 28, 813;
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37049070053
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For analogous reactivity of alkenes, see
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b) R. Grigg, T. R. Perrior, G. J. Sexton, S. Surendrakumar, T. Suzuki, J. Chem. Soc. Chem. Commun. 1993, 372. For analogous reactivity of alkenes, see:
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Grigg, R.1
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d) R. Grigg, J. Markandu, S. Surendrakumar, M. Thornton-Pett, W. J. Warnock, Tetrahedron 1992, 48, 10399;
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0034670538
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e) H. A. Dondas, R. Grigg, M. Hadjisoteriou, J. Markandu, W A. Thomas, P. Kennewell, Tetrahedron 2000, 56, 10087. For analogous reactivity of alienes, see:
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60
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37049076541
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Shaw, R.1
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61
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70350027514
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After cyclization, intermediate II could be formed after deprotonation (III→IV) and isomerization (IV→II). So far, all attempts to observe reaction intermediates by NMR methods have not been fruitful.
-
After cyclization, intermediate II could be formed after deprotonation (III→IV) and isomerization (IV→II). So far, all attempts to observe reaction intermediates by NMR methods have not been fruitful.
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-
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62
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70350039396
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note
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The use of the milder reaction conditions A is generally optimal for aldoximes (which tend to decompose at higher temperatures) or for cyclization onto terminal alkynes (which are typically more facile). To provide calibration on the usual reaction conditions, substrate la provided the desired pyridine 2a in 73 % yield after 2 h as determined by NMR methods, whereas only a 14% yield was observed after 6 h at 100 °C (NMR methods). By NMR methods, most of the mass balance proved to be unreacted starting material.
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