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For an excellent overview of terms, steric constraints, and orbital overlap see
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8
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34447297704
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Repetitive alkylations consistently proceed with the same yield, accompanied by the hydroxyalkenenitrile 12 (OMgMe = OH) resulting from carbonyl addition.
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Repetitive alkylations consistently proceed with the same yield, accompanied by the hydroxyalkenenitrile 12 (OMgMe = OH) resulting from carbonyl addition.
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33
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34447294403
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12
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12
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34
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34447299001
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35
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0000526031
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The fragmentation of β-alkoxynitriles is often facile and in this instance the formation of a dioxide likely facilitates the fragmentation to an even greater extent: (a) Carrier, P. R.; Lo, C. W.-S.; Lo, M. M.-C.; Wan, N. C.; Williams, I. D. Org. Lett. 2000, 2, 2443.
-
The fragmentation of β-alkoxynitriles is often facile and in this instance the formation of a dioxide likely facilitates the fragmentation to an even greater extent: (a) Carrier, P. R.; Lo, C. W.-S.; Lo, M. M.-C.; Wan, N. C.; Williams, I. D. Org. Lett. 2000, 2, 2443.
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37
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34447306446
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X-ray crystallography of 14b, and derivatives of 14a, 14c, and 14d, confirmed the stereochemical assignments. The authors have deposited the crystallographic data with the Cambridge Crystallographic Data Center. The data can be obtained, on request, from the Director, Cambridge Crystallographic Data Center, 12 Union Road, Cambridge, CB2 1EZ, UK.
-
X-ray crystallography of 14b, and derivatives of 14a, 14c, and 14d, confirmed the stereochemical assignments. The authors have deposited the crystallographic data with the Cambridge Crystallographic Data Center. The data can be obtained, on request, from the Director, Cambridge Crystallographic Data Center, 12 Union Road, Cambridge, CB2 1EZ, UK.
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39
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34447332675
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Considerable amounts of starting oxonitrile 1c, the hydroxyalkenenitrile i, and the hydroxyalkanenitrile ii are generated, which result from incomplete conjugate addition and alkylation, respectively. (Chemical Equation Presented)
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Considerable amounts of starting oxonitrile 1c, the hydroxyalkenenitrile i, and the hydroxyalkanenitrile ii are generated, which result from incomplete conjugate addition and alkylation, respectively. (Chemical Equation Presented)
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40
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34447312742
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9
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9
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33750337500
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Fleming, F. F.; Wei, G.; Zhang, Z.; Steward, O. W. Org. Lett. 2006, 8, 4903.
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1H NMR analysis of the crude reaction mixture failed to identify any enamide.
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1H NMR analysis of the crude reaction mixture failed to identify any enamide.
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44
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13844297054
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For a preliminary account see
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For a preliminary account see: Fleming, F. F.; Zhang, Z.; Wei, G.; Steward, O. W. Org. Lett. 2005, 7, 447.
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0034639903
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N2′ alkylation: Alnajjar, M. S.; Smith, G. F.; Kuivila, H. G. J. Org. Chem. 1984, 49, 1271.
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N2′ alkylation: Alnajjar, M. S.; Smith, G. F.; Kuivila, H. G. J. Org. Chem. 1984, 49, 1271.
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48
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34447339274
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Presumably the ejection of bromide is faster than reorganization to a C-magnesiated nitrile followed by loss of bromide.
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Presumably the ejection of bromide is faster than reorganization to a C-magnesiated nitrile followed by loss of bromide.
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49
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0037162656
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Fleming, F. F.; Wang, Q.; Zhang, Z.; Steward, O. W. J. Org. Chem. 2002, 67, 5953.
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