Open Access
Molecules, volume 27, issue 2, pages 430
Bispidine Platform as a Tool for Studying Amide Configuration Stability
Krut'ko Dmitry P.
1
,
Dalinger Alexander I
1
,
Kalinin Mikhail A
1, 2
,
Gudovannyy Alexey O
1, 4
,
Ponomarev Konstantin Y
5
,
Suslov E.V.
5
,
4
Publication type: Journal Article
Publication date: 2022-01-10
PubMed ID:
35056748
Organic Chemistry
Drug Discovery
Physical and Theoretical Chemistry
Pharmaceutical Science
Molecular Medicine
Analytical Chemistry
Chemistry (miscellaneous)
Abstract
In this work, the solution conformations of seventeen 3,7-diacyl bispidines were studied by means of NMR spectroscopy including VT NMR experiments. The acyl groups included alkyl, alkenyl, aryl, hetaryl, and ferrocene moieties. The presence of syn/anti-isomers and their ratios were estimated, and some reasons explaining experimental facts were formulated. In particular, all aliphatic and heterocyclic units in the acylic R(CO) fragments led to an increased content of the syn-form in DMSO-d6 solutions. In contrast, only the anti-form was detected in DMSO-d6 and CDCl3 in the case when R = Ph, ferrocenyl, (R)-myrtenyl. In the case of a chiral compound derived from the natural terpene myrtene, a new dynamic process was found in addition to the expected inversion around the amide N-C(O) bond. Here, rotation around the CO-C=C bond in the acylic R fragment was detected, and its energy was estimated. For this compound, ΔG for amide N-C(O) inversion was found to be equal to 15.0 ± 0.2 kcal/mol, and for the rotation around the N(CO)–C2′ bond, it was equal to 15.6 ± 0.3 kcal/mol. NMR analysis of the chiral bispidine-based bis-amide was conducted for the first time. Two X-ray structures are reported. For the first time, the unique syn-form was found in the crystal of an acyclic bispidine-based bis-amide. Quantum chemical calculations revealed the unexpected mechanism for amide bond inversion. It was found that the reaction does not proceed as direct N-C(O) bond inversion in the double-chair (CC) conformation but rather requires the conformational transformation into the chair–boat (CB) form first. The amide bond inversion in the latter requires less energy than in the CC form.
Citations by journals
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Molecules
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1 publication, 14.29%
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Russian Journal of Organic Chemistry
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Citations by publishers
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Multidisciplinary Digital Publishing Institute (MDPI)
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2 publications, 28.57%
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American Chemical Society (ACS)
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2 publications, 28.57%
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Krut'ko D. P. et al. Bispidine Platform as a Tool for Studying Amide Configuration Stability // Molecules. 2022. Vol. 27. No. 2. p. 430.
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Krut'ko D. P., Medvedko A. V., Lyssenko K. A., Churakov A. V., Dalinger A. I., Kalinin M. A., Gudovannyy A. O., Ponomarev K. Y., Suslov E., Vatsadze S. Z. Bispidine Platform as a Tool for Studying Amide Configuration Stability // Molecules. 2022. Vol. 27. No. 2. p. 430.
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TY - JOUR
DO - 10.3390/molecules27020430
UR - https://doi.org/10.3390%2Fmolecules27020430
TI - Bispidine Platform as a Tool for Studying Amide Configuration Stability
T2 - Molecules
AU - Krut'ko, Dmitry P.
AU - Lyssenko, Konstantin A.
AU - Dalinger, Alexander I
AU - Gudovannyy, Alexey O
AU - Ponomarev, Konstantin Y
AU - Medvedko, Alexey V
AU - Churakov, Andrei V.
AU - Kalinin, Mikhail A
AU - Suslov, E.V.
AU - Vatsadze, Sergey Z.
PY - 2022
DA - 2022/01/10 00:00:00
PB - Multidisciplinary Digital Publishing Institute (MDPI)
SP - 430
IS - 2
VL - 27
PMID - 35056748
SN - 1420-3049
ER -
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@article{2022_Krut'ko,
author = {Dmitry P. Krut'ko and Konstantin A. Lyssenko and Alexander I Dalinger and Alexey O Gudovannyy and Konstantin Y Ponomarev and Alexey V Medvedko and Andrei V. Churakov and Mikhail A Kalinin and E.V. Suslov and Sergey Z. Vatsadze},
title = {Bispidine Platform as a Tool for Studying Amide Configuration Stability},
journal = {Molecules},
year = {2022},
volume = {27},
publisher = {Multidisciplinary Digital Publishing Institute (MDPI)},
month = {jan},
url = {https://doi.org/10.3390%2Fmolecules27020430},
number = {2},
pages = {430},
doi = {10.3390/molecules27020430}
}
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Krut'ko, Dmitry P., et al. “Bispidine Platform as a Tool for Studying Amide Configuration Stability.” Molecules, vol. 27, no. 2, Jan. 2022, p. 430. https://doi.org/10.3390%2Fmolecules27020430.