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An interesting related process involving acylcyanides in place of aldehydes has been described: Oaksmith, J. M, Peters, U, Ganem, B. J. Am. Chem. Soc. 2004, 126, 13606
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An interesting related process involving acylcyanides in place of aldehydes has been described: Oaksmith, J. M.; Peters, U.; Ganem, B. J. Am. Chem. Soc. 2004, 126, 13606.
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The O, N-acyl migration in an O-acyl isopeptide has been exploited for the synthesis of an amyloid β-peptide, see: Skwarczynski, M.; Kiso, Y. Curr. Med. Chem. 2007, 14, 2813, and references cited therein.
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In related work (unpublished), racemization occurred during the preparation of the ester isonitrile from enantiomerically pure L-N-formyl-Phe-OMe in our hands; for similar problems, see: Bon, R. S.; Hong, C.; Bouma, M. J.; Schmitz, R. F.; De Kanter, F. J. J.; Lutz, M.; Spek, A. L.; Orru, R. V. A. Org. Lett. 2003, 5, 3759. We therefore verified that no such problems arose for amide isonitriles, such as 10a and 10b, using a known model amide isonitrile. See the Supporting Information for details.
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In related work (unpublished), racemization occurred during the preparation of the ester isonitrile from enantiomerically pure L-N-formyl-Phe-OMe in our hands; for similar problems, see: Bon, R. S.; Hong, C.; Bouma, M. J.; Schmitz, R. F.; De Kanter, F. J. J.; Lutz, M.; Spek, A. L.; Orru, R. V. A. Org. Lett. 2003, 5, 3759. We therefore verified that no such problems arose for amide isonitriles, such as 10a and 10b, using a known model amide isonitrile. See the Supporting Information for details.
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1H NMR spectral analysis. Subsequent analysis of product 15, derived from 13c, confirmed that the dr was low (vide infra). For an enantioselective catalytic P-3CR and leading references on diastereoselective P-3CR, see: Wang, S.-X.; Wang, M.-X.; Wang, D.-X.; Zhu, J. Angew. Chem., Int. Ed. 2008, 47, 388.
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1H NMR spectral analysis. Subsequent analysis of product 15, derived from 13c, confirmed that the dr was low (vide infra). For an enantioselective catalytic P-3CR and leading references on diastereoselective P-3CR, see: Wang, S.-X.; Wang, M.-X.; Wang, D.-X.; Zhu, J. Angew. Chem., Int. Ed. 2008, 47, 388.
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This transformation proved to be difficult to monitor by TLC (identical Rf values) and 1H NMR presence of diastereoisomers and rotamers
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1H NMR (presence of diastereoisomers and rotamers).
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