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Our papers in relation to optically active atropisomeric anilides:
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Papers in relation to optically active atropisomeric anilides
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N,N-Dialkyl 2,6-disubstituted aromatic amides are also known to exist as stable nonbiaryl atropisomeric compounds at room temperature. Recently, the stereoselective synthesis of optically active forms of these compounds has been reported by several groups.
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As far as we know, Pd-catalyzed N-arylation with ortho-alkylated anilide derivatives has not been reported.
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note
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-1 (85.1 °C). These data were subjected to an Eyring plot to determine the rotational barrier of the racemization.
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66
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33749512894
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See Supporting Information in preliminary Communication (ref 12).
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Among the N-nitrophenylated products 2a-r, only the NMR spectrum of benzanilide 2m showed a broadening of the signals which may be due to the equilibrium between the E- and Z-rotames.
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69
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33749511710
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1H NMR chart of 2a, 6a-8a at room temperature and 223 K (-50 °C) are shown in Supporting Information.
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All calculations were carried out by using GAMESS (US) package. Schmidt, M. W.; Baldridge, K. K.; Elbert, Gordon, M. S.; Jensen, J. H.; Koseki, S.; Matsunaga, N.; Nguyen, K. A.; Su, S. J.; Windus, T. L.; Dupuis, M.; Montgomery, J. M. J. Comput. Chem. 1993, 14, 1347.
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NOESY experiment of 6a was not investigated because of an overlap of the ortho-hydrogen (Hc) in the N-phenyl group with an other aromatic hydrogen.
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note
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In a previous paper (ref 5f). we reported that the larger bond angle [C(O)-N-C] of a six-membered lactam than that of a five-membered lactam resulted in a higher rotational barrier around the N-Ar bond.
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