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- Publisher Website: 10.1039/p19770001756
- Scopus: eid_2-s2.0-0017522327
- PMID: 561110
- WOS: WOS:A1977DT13000013
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Article: To enzyme analogues by lock and key chemistry with crown compounds. Part 1. Enantiomeric differentiation by configurationally chiral cryptands synthesised from L-tartaric acid and D-mannitol
Title | To enzyme analogues by lock and key chemistry with crown compounds. Part 1. Enantiomeric differentiation by configurationally chiral cryptands synthesised from L-tartaric acid and D-mannitol |
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Authors | |
Issue Date | 1977 |
Citation | Journal of the Chemical Society, Perkin Transactions 1, 1977, n. 15, p. 1756-1769 How to Cite? |
Abstract | The requirements of an enzyme analogue are discussed in terms of (i) binding, (ii) chirality, and (iii) functionality The ability of 18-crown-6 derivatives to complex with primary alkylammonium cations indicates the potential of the 18-crown-6 constitution to provide the binding requirement of an enzyme analogue. Attention is drawn to the fact that carbohydrates provide not only functionality but also a relatively inexpensive source of chiral bismethylene-dioxy units for incorporation into the 18-crown-6 framework. The optically pure configurationally chiral cryptands L-(14). LL-(15). LL-(16), LL-(17), DD-(17), LL-(18), DD-(28), D-(29), DDD-(30), DD-(31), DD-(32), and DD-(33) have been synthesised from L-tartaric acid and D-mannitol. The 18-crown-6 locks excluding the tetraol LL-(16) and the octaol DD-(31 ), have been shown by 1H n.m.r. spectroscopy to form complexes in CD 2Cl2 with primary alkylammonium salts. The stability constants for complexes formed in CDCl3 solution between (i) t-butylammonium thiocyanate and (ii) benzylammonium thiocyanate and some of these 18-crown-6 locks have been determined by an 1H n.m.r. spectroscopic method and compared with the complexing ability of 18-crown-6 (34). 1H and 13C N.m.r. spectroscopy has been used to demonstrate that the locks LL-(18) and DD-(28) exhibit enantiomeric differentiation in complexation equilibria towards (RS)-a-phenylethylammonium hexafluorophosphate [(RS)-(8),HPF6]. The tetraol LL-(16) and the octaol DD-(31) have been shown by 1H n.m.r. spectroscopy to form complexes in CD8OD and D2O with primary alkylammonium salts. The tetra-O-isopropylidene derivative DD-(28) forms strong complexes in methanolic solution with alkali metal cations. |
Persistent Identifier | http://hdl.handle.net/10722/332342 |
ISSN | |
ISI Accession Number ID |
DC Field | Value | Language |
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dc.contributor.author | Curtis, W. David | - |
dc.contributor.author | Laidler, Dale A. | - |
dc.contributor.author | Stoddart, J. Fraser | - |
dc.contributor.author | Jones, Graham H. | - |
dc.date.accessioned | 2023-10-06T05:10:42Z | - |
dc.date.available | 2023-10-06T05:10:42Z | - |
dc.date.issued | 1977 | - |
dc.identifier.citation | Journal of the Chemical Society, Perkin Transactions 1, 1977, n. 15, p. 1756-1769 | - |
dc.identifier.issn | 1472-7781 | - |
dc.identifier.uri | http://hdl.handle.net/10722/332342 | - |
dc.description.abstract | The requirements of an enzyme analogue are discussed in terms of (i) binding, (ii) chirality, and (iii) functionality The ability of 18-crown-6 derivatives to complex with primary alkylammonium cations indicates the potential of the 18-crown-6 constitution to provide the binding requirement of an enzyme analogue. Attention is drawn to the fact that carbohydrates provide not only functionality but also a relatively inexpensive source of chiral bismethylene-dioxy units for incorporation into the 18-crown-6 framework. The optically pure configurationally chiral cryptands L-(14). LL-(15). LL-(16), LL-(17), DD-(17), LL-(18), DD-(28), D-(29), DDD-(30), DD-(31), DD-(32), and DD-(33) have been synthesised from L-tartaric acid and D-mannitol. The 18-crown-6 locks excluding the tetraol LL-(16) and the octaol DD-(31 ), have been shown by 1H n.m.r. spectroscopy to form complexes in CD 2Cl2 with primary alkylammonium salts. The stability constants for complexes formed in CDCl3 solution between (i) t-butylammonium thiocyanate and (ii) benzylammonium thiocyanate and some of these 18-crown-6 locks have been determined by an 1H n.m.r. spectroscopic method and compared with the complexing ability of 18-crown-6 (34). 1H and 13C N.m.r. spectroscopy has been used to demonstrate that the locks LL-(18) and DD-(28) exhibit enantiomeric differentiation in complexation equilibria towards (RS)-a-phenylethylammonium hexafluorophosphate [(RS)-(8),HPF6]. The tetraol LL-(16) and the octaol DD-(31) have been shown by 1H n.m.r. spectroscopy to form complexes in CD8OD and D2O with primary alkylammonium salts. The tetra-O-isopropylidene derivative DD-(28) forms strong complexes in methanolic solution with alkali metal cations. | - |
dc.language | eng | - |
dc.relation.ispartof | Journal of the Chemical Society, Perkin Transactions 1 | - |
dc.title | To enzyme analogues by lock and key chemistry with crown compounds. Part 1. Enantiomeric differentiation by configurationally chiral cryptands synthesised from L-tartaric acid and D-mannitol | - |
dc.type | Article | - |
dc.description.nature | link_to_subscribed_fulltext | - |
dc.identifier.doi | 10.1039/p19770001756 | - |
dc.identifier.pmid | 561110 | - |
dc.identifier.scopus | eid_2-s2.0-0017522327 | - |
dc.identifier.issue | 15 | - |
dc.identifier.spage | 1756 | - |
dc.identifier.epage | 1769 | - |
dc.identifier.isi | WOS:A1977DT13000013 | - |