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- Publisher Website: 10.1002/chem.19970030818
- Scopus: eid_2-s2.0-0030794768
- WOS: WOS:A1997XR09000015
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Article: Achiral cycledextrin analogues
Title | Achiral cycledextrin analogues |
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Authors | |
Keywords | Analogues Carbohydrates Cyclodextrin Cyclooligomerizations Glycosylations Nan ostructures |
Issue Date | 1997 |
Citation | Chemistry - A European Journal, 1997, v. 3, n. 8, p. 1299-1314 How to Cite? |
Abstract | The synthesis of a new family of cycledextrin (CD) analogues is described. This family consists of novel cyclic oligosaccharides built from monosaccharides that possess the same relative but opposite absolute (D- and L-) configurations. The alternation of such D- and L-residues-specifically, D- and L-rhamnose or D- and L-mannose-in a macrocyclic structure results in S(n)-type symmetry and, consequently, optical inactivity. The synthesis of these cyclic oligosaccharides was achieved by an economical polycondensation/cycloglycosylation approach that relies on an appropriately-derivatized disaccharide monomer and that avoids the time-consuming, and often low-yielding, stepwise growth of long linear oligosaccharide precursors. In the cases reported, the key precursors are the disaccharide menumars 1-RR and 1-MM, which bear both a glycosyl donor (cyanoethylidene function) and a glycosyl acceptor (trity1oxy group). These compounds are able to undergo Tr+-catalyzed polycondensation which, under appropriate dilution conditions, can be terminated by cycloglycosylation. Thus, compound 1-RR was converted into a range of protected cyclic rhamnooligosaccharides 15-19 in 64% overall yield. All these products, including the unique cyclic dodeca- and tetradecasaccharides 18 and 19, have been isolated by preparative HPLC. Unexpectedly, treatment of the manno analogue of thedisaccharide 1-RR (compound 1-MM) under the same conditions produced only the cyclic hexasaccharide 28 and numerous apparently linear oligomers. Removal of the protecting groups from 16-19 afforded the free cyclic oligosaccharides 2124, which exhibited the predicted zero optical rotation and very simple NMR spectra, indicating highly symmetrical structures. X-ray crystallography reveals that in the solid state the cyclooctaoside 21 possesses a C2 symmetric structure, on account of a slight deformation of its cylindrical shape. The channel-type crystal packing of molecules of 21 forms nanotubes with an internal diameter of around 1 nm. Conversely, the cyclic hexasaccharide 29 possesses a C symmetric solid-state structure and its molecules pack to form a parquet-like superstructure. |
Persistent Identifier | http://hdl.handle.net/10722/332397 |
ISSN | 2023 Impact Factor: 3.9 2023 SCImago Journal Rankings: 1.058 |
ISI Accession Number ID |
DC Field | Value | Language |
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dc.contributor.author | Ashton, Peter R. | - |
dc.contributor.author | Cantrill, Stuart J. | - |
dc.contributor.author | Gattuso, Giuseppe | - |
dc.contributor.author | Menzer, Stephan | - |
dc.contributor.author | Nepogodiev, Sergey A. | - |
dc.contributor.author | Shipway, Andrew N. | - |
dc.contributor.author | Stoddart, J. Fraser | - |
dc.contributor.author | Williams, David J. | - |
dc.date.accessioned | 2023-10-06T05:11:09Z | - |
dc.date.available | 2023-10-06T05:11:09Z | - |
dc.date.issued | 1997 | - |
dc.identifier.citation | Chemistry - A European Journal, 1997, v. 3, n. 8, p. 1299-1314 | - |
dc.identifier.issn | 0947-6539 | - |
dc.identifier.uri | http://hdl.handle.net/10722/332397 | - |
dc.description.abstract | The synthesis of a new family of cycledextrin (CD) analogues is described. This family consists of novel cyclic oligosaccharides built from monosaccharides that possess the same relative but opposite absolute (D- and L-) configurations. The alternation of such D- and L-residues-specifically, D- and L-rhamnose or D- and L-mannose-in a macrocyclic structure results in S(n)-type symmetry and, consequently, optical inactivity. The synthesis of these cyclic oligosaccharides was achieved by an economical polycondensation/cycloglycosylation approach that relies on an appropriately-derivatized disaccharide monomer and that avoids the time-consuming, and often low-yielding, stepwise growth of long linear oligosaccharide precursors. In the cases reported, the key precursors are the disaccharide menumars 1-RR and 1-MM, which bear both a glycosyl donor (cyanoethylidene function) and a glycosyl acceptor (trity1oxy group). These compounds are able to undergo Tr+-catalyzed polycondensation which, under appropriate dilution conditions, can be terminated by cycloglycosylation. Thus, compound 1-RR was converted into a range of protected cyclic rhamnooligosaccharides 15-19 in 64% overall yield. All these products, including the unique cyclic dodeca- and tetradecasaccharides 18 and 19, have been isolated by preparative HPLC. Unexpectedly, treatment of the manno analogue of thedisaccharide 1-RR (compound 1-MM) under the same conditions produced only the cyclic hexasaccharide 28 and numerous apparently linear oligomers. Removal of the protecting groups from 16-19 afforded the free cyclic oligosaccharides 2124, which exhibited the predicted zero optical rotation and very simple NMR spectra, indicating highly symmetrical structures. X-ray crystallography reveals that in the solid state the cyclooctaoside 21 possesses a C2 symmetric structure, on account of a slight deformation of its cylindrical shape. The channel-type crystal packing of molecules of 21 forms nanotubes with an internal diameter of around 1 nm. Conversely, the cyclic hexasaccharide 29 possesses a C symmetric solid-state structure and its molecules pack to form a parquet-like superstructure. | - |
dc.language | eng | - |
dc.relation.ispartof | Chemistry - A European Journal | - |
dc.subject | Analogues | - |
dc.subject | Carbohydrates | - |
dc.subject | Cyclodextrin | - |
dc.subject | Cyclooligomerizations | - |
dc.subject | Glycosylations | - |
dc.subject | Nan ostructures | - |
dc.title | Achiral cycledextrin analogues | - |
dc.type | Article | - |
dc.description.nature | link_to_subscribed_fulltext | - |
dc.identifier.doi | 10.1002/chem.19970030818 | - |
dc.identifier.scopus | eid_2-s2.0-0030794768 | - |
dc.identifier.volume | 3 | - |
dc.identifier.issue | 8 | - |
dc.identifier.spage | 1299 | - |
dc.identifier.epage | 1314 | - |
dc.identifier.isi | WOS:A1997XR09000015 | - |