A Convergent Synthesis of a Carbohydrate-Containing Dendrimer

Angewandte Chemie (International Edition in English)

Volumn 36, Issue 7, 1997, Pages 732-735

  Ashton, Peter R ^a   Boyd, Sue E ^a   Brown, Christopher L ^a   Jayaraman, Narayanaswamy ^a   Fraser Stoddart, J ^a  

^a UNIVERSITY OF BIRMINGHAM   (United Kingdom)

Author keywords

Carbohydrates; Dendrimers; Glycoconjugates; Glycosides

Indexed keywords

EID: 0030803087     PISSN: 05700833     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.199707321     Document Type: Article

References (34)

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17. Examples of multiple saccharides carrying polymers and their biological activities: a) S. Sabesan, J. Düus, S. Neira, P. Domaille, S. Keim, J. C. Paulson, K. Bock, J. Am. Chem. Soc. 1992, 114, 8363-8375; b) R. Roy, F. D. Tropper, A. Romanowska, J. Chem. Soc. Chem. Commun. 1992, 1611-1613; c) S. I. Nishimura, T. Furuike, K. Matsuoka, K. Maruyama, K. Nagata, K. Kurita, N. Nishi, S. Tokura, Macromolecules 1994, 27, 4876-4880; d) G. B. Sigal, M. Mammen, G. Dahmann, G. M. Whitesides, J. Am. Chem. Soc. 1996, 118, 3789-3800; e) K. H. Mortell, R. S. Weathermann, L. L. Kiessling, ibid. 1996, 118, 2297-2298.
18. Examples of multiple saccharides carrying polymers and their biological activities: a) S. Sabesan, J. Düus, S. Neira, P. Domaille, S. Keim, J. C. Paulson, K. Bock, J. Am. Chem. Soc. 1992, 114, 8363-8375; b) R. Roy, F. D. Tropper, A. Romanowska, J. Chem. Soc. Chem. Commun. 1992, 1611-1613; c) S. I. Nishimura, T. Furuike, K. Matsuoka, K. Maruyama, K. Nagata, K. Kurita, N. Nishi, S. Tokura, Macromolecules 1994, 27, 4876-4880; d) G. B. Sigal, M. Mammen, G. Dahmann, G. M. Whitesides, J. Am. Chem. Soc. 1996, 118, 3789-3800; e) K. H. Mortell, R. S. Weathermann, L. L. Kiessling, ibid. 1996, 118, 2297-2298.
19. Examples of multiple saccharides carrying polymers and their biological activities: a) S. Sabesan, J. Düus, S. Neira, P. Domaille, S. Keim, J. C. Paulson, K. Bock, J. Am. Chem. Soc. 1992, 114, 8363-8375; b) R. Roy, F. D. Tropper, A. Romanowska, J. Chem. Soc. Chem. Commun. 1992, 1611-1613; c) S. I. Nishimura, T. Furuike, K. Matsuoka, K. Maruyama, K. Nagata, K. Kurita, N. Nishi, S. Tokura, Macromolecules 1994, 27, 4876-4880; d) G. B. Sigal, M. Mammen, G. Dahmann, G. M. Whitesides, J. Am. Chem. Soc. 1996, 118, 3789-3800; e) K. H. Mortell, R. S. Weathermann, L. L. Kiessling, ibid. 1996, 118, 2297-2298.
20. Examples of multiple saccharides carrying polymers and their biological activities: a) S. Sabesan, J. Düus, S. Neira, P. Domaille, S. Keim, J. C. Paulson, K. Bock, J. Am. Chem. Soc. 1992, 114, 8363-8375; b) R. Roy, F. D. Tropper, A. Romanowska, J. Chem. Soc. Chem. Commun. 1992, 1611-1613; c) S. I. Nishimura, T. Furuike, K. Matsuoka, K. Maruyama, K. Nagata, K. Kurita, N. Nishi, S. Tokura, Macromolecules 1994, 27, 4876-4880; d) G. B. Sigal, M. Mammen, G. Dahmann, G. M. Whitesides, J. Am. Chem. Soc. 1996, 118, 3789-3800; e) K. H. Mortell, R. S. Weathermann, L. L. Kiessling, ibid. 1996, 118, 2297-2298.
21. Examples of multiple saccharides carrying polymers and their biological activities: a) S. Sabesan, J. Düus, S. Neira, P. Domaille, S. Keim, J. C. Paulson, K. Bock, J. Am. Chem. Soc. 1992, 114, 8363-8375; b) R. Roy, F. D. Tropper, A. Romanowska, J. Chem. Soc. Chem. Commun. 1992, 1611-1613; c) S. I. Nishimura, T. Furuike, K. Matsuoka, K. Maruyama, K. Nagata, K. Kurita, N. Nishi, S. Tokura, Macromolecules 1994, 27, 4876-4880; d) G. B. Sigal, M. Mammen, G. Dahmann, G. M. Whitesides, J. Am. Chem. Soc. 1996, 118, 3789-3800; e) K. H. Mortell, R. S. Weathermann, L. L. Kiessling, ibid. 1996, 118, 2297-2298.
22. P. R. Ashton, S. E. Boyd, C. L. Brown, N. Jayaraman, S. A. Nepogodiev, J. F. Stoddart, Chem. Eur. J. 1996, 2, 1115-1128.
23. Because of the difficulties in naming these mixed generation dendrimers by the notation recommended for uniform dendrimers (G. R. Newkome, G. R. Baker, J. K. Young, J. G. Traynham, J. Polym. Sci. Part A: Polym. Chem. 1993, 31, 641-651), we denote them simply as "n-mers" to indicate the presence of n peripheral monosaccharide units.
24. 3N, was hydrolyzed with aqueous 2M NaOH and MeOH to afford 2 (72%) as a foamy solid.
25. 2 atmosphere. The reaction mixture was stirred at room temperature for 5 days, filtered, und worked up as described for 5 (see Experimental Section).
26. 2O as eluant.
27. MALDI-TOF mass spectra were obtained with either 2,5-dihydroxy benzoic acid (gentistic acid) or trans-3-indoleacrylic acid and an average of 50 laser shots per sample.
28. 1H NMR timescale.
29. 13C NMR spectra. At present these peaks are presumed to arise from an impurity.
30. 3 at 389 K, revealed the presence of four resonances (major δ = 1.424 and 1.418, minor d = 1.412 and 1.405) arising from the tert-butyl groups. This observation not only suggests that there are constitutional isomers as a result of disposition of the wedge around the core in the 24-mer, but also that the tert-butyl groups in the 24-mer residue are in two different environments. This is perhaps due to increased restriction of rotation about the tertiary amide bonds at its highly hindered core.
31. α-(benzyloxycarbonyl)glycinamido]-3,3′-bis(propionic acid) [5] with two equivalents of the amine 3,3′-iminobis(methylpropionate) followed by hydrolysis of the methyl ester functions.
32. + ion assisted laser desorption : Z. Xu, M. Kahr, K. L. Walker, C. L. Wilkins, J. S. Moore, J. Am. Chem. Soc. 1994, 116, 4537-4550. Although peaks were observed in the molecular ion regions for the free saccharide-containing dendrimers named above, the spectra were complex, presumably due to the use of silver salts.
33. Molecular simulations were carried out as described previously [5], with the exception that the molecular volume calculations were performed with Biosym's Insight and Discover software (Biosym Technologies, San Diego, CA) on a Silicon graphics Indy workstation.
34. 1H NMR chemical shifts.