TY - JOUR
T1 - Frustrated Helicity
T2 - Joining the Diverging Ends of a Stable Aromatic Amide Helix to Form a Fluxional Macrocycle
AU - Urushibara, Ko
AU - Ferrand, Yann
AU - Liu, Zhiwei
AU - Masu, Hyuma
AU - Pophristic, Vojislava
AU - Tanatani, Aya
AU - Huc, Ivan
N1 - Funding Information:
This work was partly supported by JSPS KAKENHI Grant No 16K08318 (to A.T.) and 17J00036 (to K.U.). A.T. gratefully acknowledges funding from The Sumitomo Foundation and The Naito Foundation. Computational work was supported by NSF grant MRI CHE-1229564. We thank Dr. B. Kauffmann for assistance of X-ray crystallographic analysis.
Publisher Copyright:
© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
PY - 2018/6/25
Y1 - 2018/6/25
N2 - Macrocyclization of a stable two-turn helical aromatic pentamide, that is, an object with diverging ends that are not prone to cyclization, was made possible by the transient introduction of disruptors of helicity in the form of acid-labile dimethoxybenzyl tertiary amide substituents. After removal of the helicity disruptors, NMR, X-ray crystallography, and computational studies show that the macrocycle possesses a strained structure that tries to gain as high a helical content as possible despite being cyclic. Two points of disruption of helicity remain, in particular a cis amide bond. This point of disruption of helicity can propagate along the cycle in a fluxional manner according to defined trajectories to produce ten degenerate conformations.
AB - Macrocyclization of a stable two-turn helical aromatic pentamide, that is, an object with diverging ends that are not prone to cyclization, was made possible by the transient introduction of disruptors of helicity in the form of acid-labile dimethoxybenzyl tertiary amide substituents. After removal of the helicity disruptors, NMR, X-ray crystallography, and computational studies show that the macrocycle possesses a strained structure that tries to gain as high a helical content as possible despite being cyclic. Two points of disruption of helicity remain, in particular a cis amide bond. This point of disruption of helicity can propagate along the cycle in a fluxional manner according to defined trajectories to produce ten degenerate conformations.
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U2 - 10.1002/anie.201802159
DO - 10.1002/anie.201802159
M3 - Article
C2 - 29655204
AN - SCOPUS:85048779247
SN - 1433-7851
VL - 57
SP - 7888
EP - 7892
JO - Angewandte Chemie - International Edition
JF - Angewandte Chemie - International Edition
IS - 26
ER -