Por favor, use este identificador para citar o enlazar a este item:
http://hdl.handle.net/10261/272946
COMPARTIR / EXPORTAR:
SHARE CORE BASE | |
Visualizar otros formatos: MARC | Dublin Core | RDF | ORE | MODS | METS | DIDL | DATACITE | |
Título: | Understanding the unusual regioselectivity in the nucleophilic ring-opening reactions of gem-disubstituted cyclic sulfates. Experimental and theoretical studies |
Autor: | Avenoza, Alberto; Busto, Jesús H.; Corzana, Francisco; García, José I. CSIC ORCID ; Peregrina, Jesús M. | Fecha de publicación: | 2003 | Editor: | American Chemical Society | Citación: | Journal of Organic Chemistry 68(11): 4506-4513 (2003) | Resumen: | The regioselectivity of the nucleophilic ring-opening reactions of three gem-disubstituted cyclic sulfates with sodium azide has been studied from both experimental and theoretical viewpoints. It is found that, depending on the substituent present in the cyclic sulfate, the reaction displays reversed regioselectivity, which allows one or another regioisomer to be obtained with selectivities greater than 4:1. The theoretical calculations show that, contrary to previous understanding, the intrinsic preference in all cases is azide attack at the less-substituted Cβ position, a consequence of similar stereoelectronic effects in the three sulfates considered. The observed preference for Cα attack in the case of the ester sulfate is explained in terms of differential solvent effects, which are in turn due to subtle differences in the charge transfer in the different transition structures. | Versión del editor: | https://doi.org/10.1021/jo034178q | URI: | http://hdl.handle.net/10261/272946 | DOI: | 10.1021/jo034178q | ISSN: | 0022-3263 |
Aparece en las colecciones: | (ICMA) Artículos |
Ficheros en este ítem:
Fichero | Descripción | Tamaño | Formato | |
---|---|---|---|---|
accesoRestringido.pdf | 59,24 kB | Adobe PDF | Visualizar/Abrir |
CORE Recommender
SCOPUSTM
Citations
18
checked on 06-abr-2024
WEB OF SCIENCETM
Citations
17
checked on 22-feb-2024
Page view(s)
42
checked on 23-abr-2024
Download(s)
8
checked on 23-abr-2024
Google ScholarTM
Check
Altmetric
Altmetric
NOTA: Los ítems de Digital.CSIC están protegidos por copyright, con todos los derechos reservados, a menos que se indique lo contrario.