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33746797651
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The reaction scheme presented is strictly correct only for sterically unhindered acyl donors, where the catalytic route is considerably faster than the uncatalyzed reaction
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Fischer C.B., Xu S., and Zipse H. Chem. Eur. J. 12 (2006) 5779-5784 The reaction scheme presented is strictly correct only for sterically unhindered acyl donors, where the catalytic route is considerably faster than the uncatalyzed reaction
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8444241193
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The acylpyridinium salt derived from DMAP has a higher solubility than that from pyridine, and this could also contribute to its greater effectiveness
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Pascal, R. A. Jr., Personal communication. DFT calculations for 3 were performed by using gaussian-98; the built-in default thresholds for wavefunction and gradient convergence were employed. Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Zakrzewski, V. G.; Montgomery, J. A., Jr.; Stratmann, R. E.; Burant, J. C.; Dapprich, S.; Millam, J. M.; Daniels, A. D.; Kudin, K. N.; Strain, M. C.; Farkas, O.; Tomasi, J.; Barone, V.; Cossi, M.; Cammi, M. R.; Mennucci, B.; Pomelli, C.; Adamo, C.; Clifford, S.; Ochterski, J.; Petersson, G. A.; Ayala, P. Y.; Cui, Q.; Morokuma, K.; Salvador, P.; Dannenberg, J. J.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman, J. B.; Cioslowski, J.; Ortiz, J. V.; Baboul, A. G.; Stefanov, B. B.; Liu, G. A.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Gomperts, R.; Martin, R. L.; Fox, D. J.; Keith, T.; Al-Laham, M. A.; Peng, C. Y.; Nanayakkara, A.; Challacombe, M.; Gill, P. M. W.; Johnson, B.; Chen, W.; Wong, M. W.; Andres, J. L.; Gonzalez, C.; Head-Gordon, M.; Replogle, E. S.; Pople, J. A. gaussian-98 (Revision A. 7), Gaussian, Pittsburgh, PA, 2001.
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37
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33846915546
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note
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While 4-N lone pair orbital parallel to the π system is beneficial for the first step, it is partially detrimental for the second step because it makes N-C{double bond, long}O bond breaking difficult, and so it is conceivable that some flexibility in the ring system might be beneficial for catalysis.
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38
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1542287633
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46
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33846924132
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note
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3OD) δ: 157.39, 148.73, 129.37, 52.17, 30.61, 26.95, 25.29.
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