Details
| Originalsprache | Englisch |
|---|---|
| Seiten (von - bis) | 2412-2425 |
| Seitenumfang | 14 |
| Fachzeitschrift | Organic and Biomolecular Chemistry |
| Jahrgang | 6 |
| Ausgabenummer | 13 |
| Publikationsstatus | Veröffentlicht - 2008 |
Abstract
Starting from quinic acid 7 the synthesis of 1,4-butanediol-linked macrocyclic aminocyclitols 30, 32, 34, 36 and 38 is described. Assembly was achieved by olefin cross-metathesis of appropriate cyclohexyl allyl ethers followed by ring-closing metathesis of bis-O-allyl homodimers. In all five cases studied, the only products that were formed were those resulting from direct ring-closing metathesis; the formation of larger rings was not detected. These macrocycles exhibited diverse conformational behaviour which included formation of stable separable conformers 31a and 31b as well as conformationally dynamic macrocycles 35 in which a ring flip in one cyclohexane chair conformer induces a ring flip of the other cyclohexane ring through the linking chains of the macrocycles. The activation energy for the inversion of the chair conformation in this process was determined to be about 38 kJ mol-1, which is about 7 kJ mol-1 lower than the activation energy for the ring flip of the unsubstituted cyclohexane ring. In all cases, the conformational studies strongly suggest that intramolecular H-bonding between 1,3-diaxially oriented amido and alcohol or ether groups exerts a decisive contribution to the overall stabilisation of the preferred cyclohexane chair conformation.
ASJC Scopus Sachgebiete
- Biochemie, Genetik und Molekularbiologie (insg.)
- Biochemie
- Chemie (insg.)
- Physikalische und Theoretische Chemie
- Chemie (insg.)
- Organische Chemie
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in: Organic and Biomolecular Chemistry, Jahrgang 6, Nr. 13, 2008, S. 2412-2425.
Publikation: Beitrag in Fachzeitschrift › Artikel › Forschung › Peer-Review
}
TY - JOUR
T1 - Synthetic and structural studies on macrocyclic amino cyclitols - Conformational chameleons
AU - Oelze, Benjamin
AU - Albert, Dieter
AU - Kirschning, Andreas
PY - 2008
Y1 - 2008
N2 - Starting from quinic acid 7 the synthesis of 1,4-butanediol-linked macrocyclic aminocyclitols 30, 32, 34, 36 and 38 is described. Assembly was achieved by olefin cross-metathesis of appropriate cyclohexyl allyl ethers followed by ring-closing metathesis of bis-O-allyl homodimers. In all five cases studied, the only products that were formed were those resulting from direct ring-closing metathesis; the formation of larger rings was not detected. These macrocycles exhibited diverse conformational behaviour which included formation of stable separable conformers 31a and 31b as well as conformationally dynamic macrocycles 35 in which a ring flip in one cyclohexane chair conformer induces a ring flip of the other cyclohexane ring through the linking chains of the macrocycles. The activation energy for the inversion of the chair conformation in this process was determined to be about 38 kJ mol-1, which is about 7 kJ mol-1 lower than the activation energy for the ring flip of the unsubstituted cyclohexane ring. In all cases, the conformational studies strongly suggest that intramolecular H-bonding between 1,3-diaxially oriented amido and alcohol or ether groups exerts a decisive contribution to the overall stabilisation of the preferred cyclohexane chair conformation.
AB - Starting from quinic acid 7 the synthesis of 1,4-butanediol-linked macrocyclic aminocyclitols 30, 32, 34, 36 and 38 is described. Assembly was achieved by olefin cross-metathesis of appropriate cyclohexyl allyl ethers followed by ring-closing metathesis of bis-O-allyl homodimers. In all five cases studied, the only products that were formed were those resulting from direct ring-closing metathesis; the formation of larger rings was not detected. These macrocycles exhibited diverse conformational behaviour which included formation of stable separable conformers 31a and 31b as well as conformationally dynamic macrocycles 35 in which a ring flip in one cyclohexane chair conformer induces a ring flip of the other cyclohexane ring through the linking chains of the macrocycles. The activation energy for the inversion of the chair conformation in this process was determined to be about 38 kJ mol-1, which is about 7 kJ mol-1 lower than the activation energy for the ring flip of the unsubstituted cyclohexane ring. In all cases, the conformational studies strongly suggest that intramolecular H-bonding between 1,3-diaxially oriented amido and alcohol or ether groups exerts a decisive contribution to the overall stabilisation of the preferred cyclohexane chair conformation.
UR - http://www.scopus.com/inward/record.url?scp=45749106701&partnerID=8YFLogxK
U2 - 10.1039/b716347a
DO - 10.1039/b716347a
M3 - Article
C2 - 18563277
AN - SCOPUS:45749106701
VL - 6
SP - 2412
EP - 2425
JO - Organic and Biomolecular Chemistry
JF - Organic and Biomolecular Chemistry
SN - 1477-0520
IS - 13
ER -