Synergistic Recognition of Halide Anions and Saccharides
117.9, 117.7, 115.8, 112.9, 104.2, 99.0, 97.0, 77.8, 77.1, 76.8, 75.2,
56.1, 55.8, 28.8, 28.7, 28.6, 20.1, 20.1, 19.9, 19.7 ppm. MALDI-
TOF-MS: m/z calcd. for C88H113N10O22Na [M + H + Na]+ 1684.8;
found 1684.7. HRMS (ESI): m/z calcd. for C88H113N10O22 [M +
H]+ 1661.8025; found 1661.8066.
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Oligomer 1b: Yield: 67 %; white solid. 1H NMR (CD2Cl2,
400 MHz): δ = 10.76 (br. s, 2 H), 10.54 (br. s, 2 H), 10.36 (br. s, 2
H), 10.31 (br. s, 2 H), 8.78 (s, 2 H), 8.74 (s, 1 H), 8.34 (d, J =
9.6 Hz, 2 H), 8.17 (m, 6 H), 8.10 (m, 14 H), 7.45 (s, 2 H), 7.39 (s,
2 H), 6.53 (s, 1 H), 6.26 (s, 2 H), 5.32 (d, J = 3.2 Hz, 4 H), 4.01 (d,
J = 6.4 Hz, 4 H), 3.84 (d, J = 6.4 Hz, 4 H), 3.68 (d, J = 6.4 Hz, 4
H), 3.62 (d, J = 6 Hz, 4 H), 2.39 (m, 2 H), 2.31 (m, 2 H), 2.01 (m,
2 H), 1.53 (m, 2 H), 1.16 (d, J = 6.4 Hz, 12 H), 1.10 (d, J = 6.4 Hz,
12 H), 0.98 (d, J = 6.8 Hz, 12 H), 0.43 (d, J = 6.8 Hz, 12 H) ppm.
13C NMR (CD2Cl2, 100 MHz): δ = 164.5, 164.0, 162.8, 162.2,
161.8, 161.4, 161.0, 160.0, 137.5, 137.3, 134.1, 134.0, 132.5, 131.7,
131.5, 131.3, 129.5, 128.5, 127.9, 127.7, 126.5, 125.7, 125.7, 125.4,
125.3, 125.1, 123.7, 118.1, 117.8, 115.2, 113.0, 112.6, 97.0, 96.7,
77.0, 76.9, 76.1, 75.3, 42.6, 28.8, 28.8, 28.7, 28.4, 19.9, 19.8, 19.5,
19.0 ppm. MALDI-TOF-MS: m/z calcd. for C106H116N10O18Na [M
+ Na]+ 1839.8; found 1839.9. HRMS (ESI): m/z calcd. for
C106H117N10O18 [M + H]+ 1817.8542; found 1817.8541.
Computational Details: DFT calculations were performed by using
the RB3LYP functional with the 3-21G basis set. Twenty pro-
cessing cores and 40 GB physical memory (Holland Computing
Centre, University of Nebraska – Lincoln) were used for each opti-
mization. Frequencies were also calculated at the same level of
theory to ensure that each stationary point corresponded to a mini-
mum on the potential energy surface. DFT has been shown to accu-
rately describe H-bonding in small molecules when large basis sets
are employed.[29] Due to the large size of this system, we employed
a relatively small basis set (3-21G). Because our focus here was on
the qualitative arrangement of the components through hydrogen
bonding, and not on a quantitative evaluation of H-bonding pa-
rameters, this approach seems reasonable. Although two dia-
stereomers are possible (due to chirality of 13 and 1a), only one
diastereomer of the complex was involved in the investigation.
When glucoside 13 was carefully positioned in the cavity of 1a·2Cl–,
the geometry of the oligomer did not converge to an open coil
structure, but rather to the closed helix as shown in Figure 8 (main
text). The relative strength of the H-bonds of (1a + 2Cl– + 13)
can be assessed by examining their bond lengths and bond angles
(Figures S31 and S32). Figures S31 and S32 indicate that the two
Cl– anions form strong H-bonds with the NH protons, and a com-
paratively weaker H-bond with the aryl proton. Furthermore, the
C4 hydroxy proton forms a relatively weak H-bond with the fold-
amer carbonyl group (atom 18), as indicated by a longer bond and
a smaller angle; it is able to form a much better intramolecular H-
bond with the C6 hydroxy group of 13.
Supporting Information (see footnote on the first page of this arti-
1
cle): Copies of H and 13C NMR spectra of 1–12, data of titration
experiments, 2D NMR, CD spectra, UV/Vis spectra and computa-
tional figures.
Acknowledgments
We thank the National Natural Science Foundation of China
(21125205) and the National Basic Research Program of China
(2009CB930802) for financial support. We would also like to thank
the University of Nebraska – Lincoln, Holland Computing Centre
for computational resources.
Eur. J. Org. Chem. 2013, 8135–8144
© 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
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