Synthesis of Crescent Aromatic Oligoamides
FIGURE 1. Design of backbone-rigidified aromatic oligoamides. (a) The three-center hydrogen bond that enforces the folding of
the designed oligamides. (b) Oligoamides consisting of meta- (B1) or meta/para-linked (B2) aminobenzoic acid residues. (c)
Oligoamides consisting of meta-linked diacid and diamine residues (C1), para-linked diamine and meta-linked diacid residues
(C2), and meta-linked diamine and para-linked diacid residues (C3).
molecules to adopt various secondary structures or to
undergo host-guest complexation.17,18 Among the re-
ported foldamer systems, aromatic oligoamides seem to
be one class of promising candidates to satisfy many of
these requirements,19 some of which have already dis-
played interesting activities.20,21
Aromatic oligoamide foldamers were constructed based
on anthranilic acids,22,23 pyridines,24,25 pyridine oxides,22
pyrazines,26 and so on. A few less studied aromatic
oligomers were designed based on ureas27 or hydrazides28
without amide linkages. â-Sheetlike structures29 and
well-defined molecular duplexes4,30-32 were established
based on the combination of both R-peptide backbone and
aromatic rings with alkoxy substituents to form adjacent
hydrogen bonding.29
In recent years we reported a class of oligoamides with
backbones that adopt well-defined, crescent conforma-
tions.4,19,35-38 These oligomers are based on aromatic
oligoamide backbones consisting of benzene rings that
are meta- or meta/para-linked by secondary amide groups.
The presence of a particularly robust three-center hy-
drogen bond4a,36 involving each of the amide groups of
these molecule leads to the rigidification of the amide
linkages and thus the oligoamide backbone. As shown
by general structure A (Figure 1a), the three-center
H-bonds are introduced by placing ether oxygens in the
vicinity of each amide hydrogen, leading to the formation
of a three-center H-bond consisting of five- and a six-
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