Strong hydrogen bonding to the amide nitrogen atom in an 'amide proton sponge': Consequences for structure and reactivity

Angewandte Chemie - International Edition

Volumn 38, Issue 6, 1999, Pages 798-800

  Cox, Christopher ^a   Wack, Harald ^a   Lectka, Thomas ^a  

^a JOHNS HOPKINS UNIVERSITY   (United States)

Author keywords

Amides; Hydrogen bonding; Naphthalenes; Proton sponges

Indexed keywords

AMIDE; NAPHTHALENE DERIVATIVE; NITROGEN; SULFONIC ACID DERIVATIVE;

ARTICLE; CHEMICAL REACTION; CHEMICAL STRUCTURE; CRYSTALLOGRAPHY; HYDROGEN BOND; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; PROTON TRANSPORT;

EID: 0033559505     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/(SICI)1521-3773(19990315)38:6<798::AID-ANIE798>3.0.CO;2-W     Document Type: Article

References (36)

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11. a value of about - 7; see: A. J. Williams, J. Am. Chem. Soc. 1976, 98, 5645-5651.
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19. See the Supporting Information for details.
20. [9]
21. The observation that the resonances for the cis and trans isomers coalesce to one upon protonation is consistent with previous reports that predict a lower barrier to rotation about the C-N bond when an amide is N-coordinated to a Lewis acid. See, for example: a) C. Cox, T. Lectka, J. Am. Chem. Soc. 1998, 120, 10660-10668; b) C. Cox, V. G. Young, Jr., T. Lectka, J. Am. Chem. Soc. 1997, 119, 2307-2308; c) C. Cox, D. Ferraris, N. N. Murthy, T. Lectka, J. Am. Chem. Soc. 1996, 118, 5332-5333.
22. The observation that the resonances for the cis and trans isomers coalesce to one upon protonation is consistent with previous reports that predict a lower barrier to rotation about the C-N bond when an amide is N-coordinated to a Lewis acid. See, for example: a) C. Cox, T. Lectka, J. Am. Chem. Soc. 1998, 120, 10660-10668; b) C. Cox, V. G. Young, Jr., T. Lectka, J. Am. Chem. Soc. 1997, 119, 2307-2308; c) C. Cox, D. Ferraris, N. N. Murthy, T. Lectka, J. Am. Chem. Soc. 1996, 118, 5332-5333.
23. The observation that the resonances for the cis and trans isomers coalesce to one upon protonation is consistent with previous reports that predict a lower barrier to rotation about the C-N bond when an amide is N-coordinated to a Lewis acid. See, for example: a) C. Cox, T. Lectka, J. Am. Chem. Soc. 1998, 120, 10660-10668; b) C. Cox, V. G. Young, Jr., T. Lectka, J. Am. Chem. Soc. 1997, 119, 2307-2308; c) C. Cox, D. Ferraris, N. N. Murthy, T. Lectka, J. Am. Chem. Soc. 1996, 118, 5332-5333.
24. a) G. A. Olah, A. M. White, D. H. O'Brien, Chem. Rev. 1970, 70, 561-591.
25. c o has been found; see A. J. Bennet, V. Somayaji, R. S. Brown, B. D. Santarsiero, J. Am. Chem. Soc. 1991, 113, 7563-7571.
26. 2 (SHELXTL-V5.0). R1=0.0704, wR2=0.1688 for 4744 reflections: the hydrogen atoms on N1A and N1B were located in the Fourier difference map and refined isotropically, all other hydrogens were placed in ideal positions and refined as riding atoms; one of the triflate anions has significant disorder caused by a rocking motion.
27. -) and CCDC-104130 (1b). Copies of the data can be obtained free of charge on application to CCDC, 12 Union Road, Cambridge CB21EZ, UK (fax: (+44)1223-336-033; e-mail: deposit@ccdc.cam.ac.uk).
28. Jeffrey's definition of a "moderately strong hydrogen bond" is inclusive of most biologically relevant interactions, such as the more common hydrogen bonding mode available to amides wherein the oxygen atom is the acceptor: see: G. A. Jeffrey, An Introduction to Hydrogen Bonding, Oxford, New York, 1997, chap. 2.
29. [14b]
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31. No transesterification products attributable to ring-opened THF were detected.
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35. H.-H. Otto, T. Schirmeister, Chem. Rev. 1997, 97, 133-171.
36. - undergoes dramatic intramolecular catalysis of amide isomerization in aqueous solution: C. Cox, H. Wack, T. Lectka, unpublished results.