A hydrogen-bonding receptor that binds cationic monosaccharides with high affinity in methanol

Shun Ichi Tamaru, Masashi Yamamoto, Seiji Shinkai, Alisher B. Khasanov, Thomas W. Bell

研究成果: ジャーナルへの寄稿学術誌査読

39 被引用数 (Scopus)


A dicarboxylate host (1) binds cationic monosaccharides such as D-glucosamine·HCl (2), D-galactosamine·HCl (3), and D-mannosamine·HCl (4) with high affinity (K1 = 8.0 × 104-2.0 × 105M-1) in methanol. In circular dichroism (CD) spectroscopy a positive exciton-coupling band was observed near 290 nm; this indicates that the saccharides are recognized by multiple point interactions. Since the corresponding neutral monosaccharides are not significantly bound, one may conclude that complex formation is primarily due to the electrostatic interaction between NH3+ in the guest and one carboxylate in the host and secondarily due to hydrogen-bonding interactions of OH groups with the other carboxylate and/or nitrogen bases. Molar ratio plots and Job plots indicate that host 1 and cationic monosaccharide guests form CD-active, pseudo-cyclic 1:1 complexes at low guest concentration followed by the formation of CD-silent, acyclic 1:2 1·saccharide complexes at high guest concentration. The possible binding modes are discussed in detail on the basis of molecular mechanics calculations and chemical shift changes in 1H NMR spectra. The results of competition experiments with several cationic reference compounds bearing fewer OH groups than 2-4 are consistent with the proposed binding model. Thus, the present study is a rare example of saccharide recognition in a protic solvent, where in general, hydrogen-bonding interactions are rarely useful because of strong solvation energy. These are apparently the strongest saccharide complexes involving noncovalent interactions between host and guest. We believe that the findings are significant as a milestone toward development of new saccharide recognition systems ultimately useful in aqueous solution.

ジャーナルChemistry - A European Journal
出版ステータス出版済み - 12月 17 2001

!!!All Science Journal Classification (ASJC) codes

  • 触媒
  • 有機化学


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