File Download
There are no files associated with this item.
Links for fulltext
(May Require Subscription)
- Publisher Website: 10.1039/P19820001637
- Scopus: eid_2-s2.0-37049111329
- WOS: WOS:A1982PC03300002
- Find via
Supplementary
- Citations:
- Appears in Collections:
Article: Conformational behaviour of medium-sized rings. Part 10. Dithiosalicylides and trithiosalicylides
Title | Conformational behaviour of medium-sized rings. Part 10. Dithiosalicylides and trithiosalicylides |
---|---|
Authors | |
Issue Date | 1982 |
Citation | Journal of the Chemical Society, Perkin Transactions 1, 1982, p. 1637-1648 How to Cite? |
Abstract | The trithiosalicylide derivatives (8)–(11) have been synthesised and shown by temperature-dependent 1H n.m.r. spectroscopy to exist in solution as ring inverting (35a) ⇌ (35b) enantiomeric helical conformations with trans-thioester linkages. The free energies of activation for these conformational changes are ca. 10 kcal mol−1higher than those for the similar process in the corresponding trisalicylides. In contrast with the trisalicylides, the trithiosalicylides can only ring invert between enantiomeric helical conformations via intermediates containing a cis-thioester linkage. The dithiosalicylide derivatives (3)–(7) have been synthesised; the temperature dependence of the 1H n.m.r. spectrum of di-o-thiothymotide (7) has been interpreted in terms of ring inversion (40a) ⇌ (40b) between enantiomeric boat conformations. Comparison of the ΔG‡value of 24.6 kcal mol−1for this conformational change with that of 17.7 kcal mol−1previously obtained for di-o-thymotide (41) suggests that cis-thioester linkages are subject to more resonance stabilisation than are cis-ester linkages. © Royal Society of Chemistry. |
Persistent Identifier | http://hdl.handle.net/10722/332809 |
ISSN | |
ISI Accession Number ID |
DC Field | Value | Language |
---|---|---|
dc.contributor.author | Guise, G. Bruce | - |
dc.contributor.author | Ollis, W. David | - |
dc.contributor.author | Peacock, Judith A. | - |
dc.contributor.author | Stephanatou, Julia Stephanidou | - |
dc.contributor.author | Stoddart, J. Fraser | - |
dc.date.accessioned | 2023-10-06T05:14:26Z | - |
dc.date.available | 2023-10-06T05:14:26Z | - |
dc.date.issued | 1982 | - |
dc.identifier.citation | Journal of the Chemical Society, Perkin Transactions 1, 1982, p. 1637-1648 | - |
dc.identifier.issn | 1470-4358 | - |
dc.identifier.uri | http://hdl.handle.net/10722/332809 | - |
dc.description.abstract | The trithiosalicylide derivatives (8)–(11) have been synthesised and shown by temperature-dependent <sup>1</sup>H n.m.r. spectroscopy to exist in solution as ring inverting (35a) ⇌ (35b) enantiomeric helical conformations with trans-thioester linkages. The free energies of activation for these conformational changes are ca. 10 kcal mol<sup>−1</sup>higher than those for the similar process in the corresponding trisalicylides. In contrast with the trisalicylides, the trithiosalicylides can only ring invert between enantiomeric helical conformations via intermediates containing a cis-thioester linkage. The dithiosalicylide derivatives (3)–(7) have been synthesised; the temperature dependence of the <sup>1</sup>H n.m.r. spectrum of di-o-thiothymotide (7) has been interpreted in terms of ring inversion (40a) ⇌ (40b) between enantiomeric boat conformations. Comparison of the ΔG<sup>‡</sup>value of 24.6 kcal mol<sup>−1</sup>for this conformational change with that of 17.7 kcal mol<sup>−1</sup>previously obtained for di-o-thymotide (41) suggests that cis-thioester linkages are subject to more resonance stabilisation than are cis-ester linkages. © Royal Society of Chemistry. | - |
dc.language | eng | - |
dc.relation.ispartof | Journal of the Chemical Society, Perkin Transactions 1 | - |
dc.title | Conformational behaviour of medium-sized rings. Part 10. Dithiosalicylides and trithiosalicylides | - |
dc.type | Article | - |
dc.description.nature | link_to_subscribed_fulltext | - |
dc.identifier.doi | 10.1039/P19820001637 | - |
dc.identifier.scopus | eid_2-s2.0-37049111329 | - |
dc.identifier.spage | 1637 | - |
dc.identifier.epage | 1648 | - |
dc.identifier.isi | WOS:A1982PC03300002 | - |