Published on Web 09/08/2004
Hydrogen Bonded Oligohydrazide Foldamers and Their
Recognition for Saccharides
Jun-Li Hou,† Xue-Bin Shao,† Guang-Ju Chen,‡ Yan-Xia Zhou,‡ Xi-Kui Jiang,† and
Zhan-Ting Li*,†
Contribution from the Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences,
354 Fenglin Lu, Shanghai 200032, China and Department of Chemistry,
Beijing Normal UniVersity, Beijing 100875, China
Received May 2, 2004; E-mail: ztli@mail.sioc.ac.cn
Abstract: This paper describes the synthesis and characterization of the first series of hydrogen bonding-
driven hydrazide foldamers and their recognition for alkyl saccharides in chloroform. Oligomers 1, 2-4, 5,
6, and 7, which contain one, two, four, six, or twelve repeated dibenzoyl hydrazide residues, respectively,
have been prepared. The rigid and planar conformations of 1 and 2 or 4 have been established with X-ray
analysis and 1H NMR spectroscopy, whereas the folding and helical conformations of 5-7 have been
evidenced by the 1D and 2D 1H NMR and IR spectroscopy and molecular mechanics calculations. Molecular
mechanics calculations also revealed that 5, 6, and 7 possess a rigid cavity with size of ca. 10.6 to 11.1
Å, and half of the carbonyl groups in the folding conformations are orientated inwardly inside the cavity. 1H
NMR and CD experiments revealed that 5-7 efficiently complex alkylated mono- and disaccharides 32-
1
35 in chloroform. The association constants (Kassoc) of the complexes have been determined with the H
NMR and fluorescent titration methods. The energy-minimized conformation of 6‚34 has been obtained
with molecular mechanics calculation. The hydrazide-based folding structures described here represent
novel examples of hydrogen bonding-driven foldamers that act as artificial receptors for selective molecular
recognition.
Introduction
tures. Examples of hydrogen (H) bonding-driven hairpin-styled
foldamers include R-peptides,7 â-peptides,8 γ-peptides,9 δ-pep-
In recent years, there has been intense interest in developing
unnatural oligomers (foldamers) that are induced by intramo-
lecular noncovalent forces to fold into well-defined secondary
structures.1 Although studies on this kind of well-defined linear
species have been initially inspired by the helical structures
found in nature, it has been expected that progress in this field
will eventually lead to unnatural macromolecules with sizes and
functions of biomacromolecules such as proteins and DNAs.1d
Among other noncovalent interactions such as metal-ligand
coordination,2 donor-acceptor interaction,3,4 and solvophobic
interaction,5,6 the hydrogen bonding motif has proven itself to
be a highly efficient tool for the formation of folding architec-
tides,10 peptdoids,11 heterocyclic ureas,12 and various peptide
analogues.13-19 A number of H-bonding-induced aromatic
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† Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences.
‡ Department of Chemistry, Beijing Normal University.
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10.1021/ja047436p CCC: $27.50 © 2004 American Chemical Society