Angewandte Chemie - International Edition, volume 52, issue 48, pages 12736-12740
Alternating asymmetric self-induction in functionalized pyrrolidine oligomers
Kudryavtsev Konstantin V.
1, 2
,
Wiedmann Steffen
4
,
Luy Burkhard
5
,
Muhle-Goll Claudia
4
,
Zefirov Nikolay S.
1, 2
,
Publication type: Journal Article
Publication date: 2013-10-10
Quartile SCImago
Q1
Quartile WOS
Q1
Impact factor: 16.6
ISSN: 14337851, 15213773
General Chemistry
Catalysis
Abstract
Artificial structurally well-defined polymers have excited interest as functional mimetics of natural biomacromolecules, exhibiting additional properties not occurring in the living world. Specific conformational organization of natural and synthetic polymeric objects leading to unique folding accounts for the molecular recognition, which is one of the driving principles in important natural processes. Some nonnatural oligomeric species adopt specific and well-defined conformations dictated by the structure of monomeric units and intramolecular interactions and are defined as foldamers. One of the most studied unnatural foldamer types are bpeptides that adopt stable folded helical, sheet, and turn-like conformations. b-Peptides are stable towards natural enzymes, and appropriate design leads to discovery of bpeptide ligands for complicated pharmaceutical targets, such as protein–protein interactions. The application of pyrrolidine-3-carboxylic acid (Pca) for the construction of bpolypeptide chain rigidifies the molecular backbone and provides additional stabilization of the secondary structure of the oligomer in solution. The typical synthesis of a b-peptide backbone is based on the arsenal of peptide chemistry methods, including routine sequences of amino group protection–deprotection steps and multiple activations of carboxylic functionality for amide bond construction. Herein we disclose a fundamentally novel synthetic method towards well-defined highly functionalized short b-peptides that avoids protection, deprotection, and activation procedures and allows to generate efficiently stereoregular oligomeric pyrrolidine-based molecules. The developed method, called cycloadditive oligomerization, has been used for the synthesis of a set of racemic and enantiopure oligomers containing a Pca backbone. The realized approach determines highly diverse structural characteristics of b-peptide oligomers, which are characterized by various physicochemical methods, including X-ray analysis. The oligomerization utilized azomethine ylide 1,3-dipolar cycloaddition as a chain-growth approach (Scheme 1). 5Arylpyrrolidine-2,4-dicarboxylate units serve both as linked elements and as auxiliaries to determine stereoand enantioselectivities of the cycloaddition process. The starting 5arylpyrrolidine-2,4-dicarboxylic acid diesters 3a (X=H, Br) for oligomer synthesis were obtained from iminoesters 1 and tert-butyl acrylate in racemic and enantiopure forms by 1,3-dipolar cycloaddition using Lewis acids for the azomethine ylide generation step (Scheme 1, Table 1). Asymmetric synthesis of the monomer ( )-3a-H was effectively conducted with the enantiopure ligand 4 on a gram scale, and single recrystallization provided the target compound with more than 99% ee. Subsequent N-acryloylation of monomers 3a with acryloyl chloride transformed them into dipolarophiles 2b with a sterically hindered amide residue connected to the ethylene fragment. We supposed that these unique dipolarophiles would induce good diastereoand enantioselectivities under iterative cycloaddition steps with iminoesters 1 (Scheme 1). Indeed, dimers 3b were effectively synthesized by cycloaddition of acrylamides 2b with Schiff bases 1 (X=H, Br) in presence of AgOAc as a Lewis acid agent for azomethine ylide generation (Table 1, entries 4–6). Comparison of H NMR spectra of the cycloaddition reaction mixtures and
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- We do not take into account publications that without a DOI.
- Statistics recalculated only for publications connected to researchers, organizations and labs registered on the platform.
- Statistics recalculated weekly.
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Kudryavtsev K. V. et al. Alternating asymmetric self-induction in functionalized pyrrolidine oligomers // Angewandte Chemie - International Edition. 2013. Vol. 52. No. 48. pp. 12736-12740.
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Kudryavtsev K. V., Ivantcova P. M., Churakov A. V., Wiedmann S., Luy B., Muhle-Goll C., Zefirov N. S., Bräse S. Alternating asymmetric self-induction in functionalized pyrrolidine oligomers // Angewandte Chemie - International Edition. 2013. Vol. 52. No. 48. pp. 12736-12740.
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TY - JOUR
DO - 10.1002/anie.201302862
UR - https://doi.org/10.1002%2Fanie.201302862
TI - Alternating asymmetric self-induction in functionalized pyrrolidine oligomers
T2 - Angewandte Chemie - International Edition
AU - Ivantcova, Polina M.
AU - Wiedmann, Steffen
AU - Zefirov, Nikolay S.
AU - Kudryavtsev, Konstantin V.
AU - Churakov, Andrei V.
AU - Luy, Burkhard
AU - Muhle-Goll, Claudia
AU - Bräse, Stefan
PY - 2013
DA - 2013/10/10 00:00:00
PB - Wiley
SP - 12736-12740
IS - 48
VL - 52
SN - 1433-7851
SN - 1521-3773
ER -
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@article{2013_Kudryavtsev,
author = {Polina M. Ivantcova and Steffen Wiedmann and Nikolay S. Zefirov and Konstantin V. Kudryavtsev and Andrei V. Churakov and Burkhard Luy and Claudia Muhle-Goll and Stefan Bräse},
title = {Alternating asymmetric self-induction in functionalized pyrrolidine oligomers},
journal = {Angewandte Chemie - International Edition},
year = {2013},
volume = {52},
publisher = {Wiley},
month = {oct},
url = {https://doi.org/10.1002%2Fanie.201302862},
number = {48},
pages = {12736--12740},
doi = {10.1002/anie.201302862}
}
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Kudryavtsev, Konstantin V., et al. “Alternating asymmetric self-induction in functionalized pyrrolidine oligomers.” Angewandte Chemie - International Edition, vol. 52, no. 48, Oct. 2013, pp. 12736-12740. https://doi.org/10.1002%2Fanie.201302862.
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