Publication
Supramolecular catalysis by cucurbit[7]uril and cyclodextrins: similarity and differences
| dc.contributor.author | Basilio, Nuno | |
| dc.contributor.author | García-Río, Luís | |
| dc.contributor.author | Moreira, José | |
| dc.contributor.author | Pessêgo, Márcia | |
| dc.date.accessioned | 2013-12-07T11:21:46Z | |
| dc.date.available | 2013-12-07T11:21:46Z | |
| dc.date.issued | 2010 | |
| dc.date.updated | 2013-12-04T18:13:17Z | |
| dc.description.abstract | To understand the analogies and differences between the cucurbituril and cyclodextrin cavities different solvolytic reactions have been studied in the presence of cucurbit[7]uril, CB7, and β-CD or its methylated derivative, DM-β-CD. Solvolysis of 1-bromoadamantane has been used as a test to evaluate the ability of the cavities to solvate the Br- leaving group. Obtained results show that in both cases the polarity inside the cavity is similar to that of a 70% ethanol:water mixture. Solvolysis of substituted benzoyl chlorides shows a great difference between the CB7 and DM-β-CD cavity. Solvolysis of electron withdrawing substituted benzoyl chlorides (associative mechanism) is catalyzed by DM-β-CD and inhibited by CB7. However, solvolysis of electron donating substituted benzoyl chlorides(dissociative mechanism) is catalyzed by CB7 and inhibited by DM-β-CD. These experimental behaviors have been explained on the basis of different solvolytic mechanisms. Participation of the hydroxyl groups of the cyclodextrin as a nucleophile can explain the catalytic effect observed for solvolysis of benzoyl chlorides reacting by an associative mechanism. Solvolysis of benzoyl chlorides reacting by a dissociative mechanism is catalyzed by CB7 due to the ability of the CB7 cavity to stabilize the acylium ion developed in the transition state by electrostatic interactions. | por |
| dc.identifier.citation | Basilio, Nuno; García-Río, Luís; Moreira, José A.; Pessêgo, Márcia. Supramolecular Catalysis by Cucurbit[7]uril and Cyclodextrins: Similarity and Differences, The Journal of Organic Chemistry, 75, 3, 848-855, 2010. | por |
| dc.identifier.doi | http://dx.doi.org/10.1021/jo902398z | |
| dc.identifier.issn | 0022-3263 | |
| dc.identifier.other | AUT: JMO01545; | |
| dc.identifier.uri | http://hdl.handle.net/10400.1/3229 | |
| dc.language.iso | eng | por |
| dc.peerreviewed | yes | por |
| dc.publisher | American Chemical Society | por |
| dc.relation.publisherversion | http://pubs.acs.org/doi/pdf/10.1021/jo902398z | por |
| dc.title | Supramolecular catalysis by cucurbit[7]uril and cyclodextrins: similarity and differences | por |
| dc.type | journal article | |
| dspace.entity.type | Publication | |
| oaire.citation.endPage | 845 | por |
| oaire.citation.issue | 3 | |
| oaire.citation.startPage | 848 | por |
| oaire.citation.title | Journal of Organic Chemistry | por |
| oaire.citation.volume | 75 | por |
| person.familyName | Moreira | |
| person.givenName | José | |
| person.identifier.ciencia-id | DC11-4E1F-F13F | |
| person.identifier.orcid | 0000-0001-8481-3436 | |
| person.identifier.rid | F-3807-2010 | |
| person.identifier.scopus-author-id | 7201506886 | |
| rcaap.rights | restrictedAccess | por |
| rcaap.type | article | por |
| relation.isAuthorOfPublication | 644799ac-df06-4840-9f12-52c5b3ff0a76 | |
| relation.isAuthorOfPublication.latestForDiscovery | 644799ac-df06-4840-9f12-52c5b3ff0a76 |
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