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a, value of the hydrogen atom at the 4-position is about 8.9.[9] Azlactones are racemized easily by external bases, but autocatalytic racemization can also occur.[10] See reference [11] for an example of the crystallization-induced generation of a diastereomerically pure azlactone.
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13444273117
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The synthesis and full characterization of the bifunctional catalysts 1a,c-g, 2, 3a,b, 4, 5a,b, 6, and 7 will be published elsewhere.
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33
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0004150157
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Kα radiation (γ = 0.71073 Å), graphite monochromator, φ/ω scans. The structure was solved by using direct methods (G. M. Sheldrick, SHELXS-97, Program for the Solution of Crystal Structures, University of Göttingen, Germany, 1997), followed by full-matrix least-squares refinement (by using all unique reflections) with anisotropic thermal parameters for non-hydrogen atoms. The positions of hydrogen atoms were refined by using a riding model (SHELXL-97). CCDC 246910 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from the Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
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Kα radiation (γ = 0.71073 Å), graphite monochromator, φ/ω scans. The structure was solved by using direct methods (G. M. Sheldrick, SHELXS-97, Program for the Solution of Crystal Structures, University of Göttingen, Germany, 1997), followed by full-matrix least-squares refinement (by using all unique reflections) with anisotropic thermal parameters for non-hydrogen atoms. The positions of hydrogen atoms were refined by using a riding model (SHELXL-97). CCDC 246910 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from the Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
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13444278666
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The urea catalyst 1a did not show a comparable increase in enantioselectivity with decreasing temperature: At 0°C the product 9e was formed with 88% ee (87% ee at room temperature; Table 1, entry 5).
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38
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13444306320
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note
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In the HPLC analysis (see Experimental Section) of the racemic azlactones 8a-f on a chiral stationary phase, equilibration of the azlactone enantiomers was clearly indicated by the peak forms typical for dynamic, interconverting analytes (see, for example. reference [30]).
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The synthesis and characterization of the diureas 11 and 12 will be reported elsewhere.
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2AQN: dihydroquinidine-(anthraquinone-1,4-diyl diether).
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