Por favor, use este identificador para citar o enlazar a este item: http://hdl.handle.net/10261/36998
COMPARTIR / EXPORTAR:
logo share SHARE logo core CORE BASE
Visualizar otros formatos: MARC | Dublin Core | RDF | ORE | MODS | METS | DIDL | DATACITE

Invitar a revisión por pares abierta
Título

Conjugate Additions of Cyclic Oxygen-Bound Nickel Enolates to α,β-Unsaturated Ketones

AutorMaya, Celia CSIC ORCID; Cámpora, Juan CSIC ORCID; Carmona, Ernesto CSIC ORCID; Matas, Inmaculada CSIC; Palma, Pilar CSIC ORCID; Gutiérrez-Puebla, Enrique CSIC ORCID; Monge, M. Ángeles CSIC ORCID
Palabras claveCycloaddition reactions
Enolates
Lactones
Metallacycles
Michael addition
Nickel
Fecha de publicación26-ene-2007
EditorWiley-VCH
CitaciónChemistry - a European Journal 13(13): 3675- 3687 (2007)
ResumenThe reaction of nickel enolates displaying a metallacyclic structure with the α,β-unsaturated ketones methyl vinyl ketone (MVK) or methyl propenyl ketone (MPK) takes place in two stages, affording initially bicyclic adducts, which subsequently isomerize to the corresponding open-chain products. The former are generated with high stereoselectivity and can be considered as the products of the [2+4] cycloaddition of the enolate to the enone. The ring opening process involves a prototropic rearrangement that can be catalyzed by water. In the case of the reaction of the parent nickel enolate complex 1 (which displays an unsubstituted Ni-O=CR)CH2 arrangement) with MVK, a double-addition process has been observed, consisting of two successive cycloaddition/isomerization reactions. The carbonylation of the different cyclic and noncyclic products affords the corresponding lactones that retain the stereochemistry of the organometallic precursors. This methodology allowed trapping the primary product of the reaction of 1 with MPK as the corresponding organic lactone, demonstrating that the cycloaddition process takes place with exo selectivity. DFT modeling of the latter reaction provides further support for a quasi-concerted cycloaddition mechanism, displaying a nonsymmetric transition state in which the C-C and the C-O bond are formed in an asynchronous manner.
Versión del editorhttp://dx.doi.org/10.1002/chem.200601357
URIhttp://hdl.handle.net/10261/36998
DOI10.1002/chem.200601357
ISSN0947-6539
E-ISSN1521-3765
Aparece en las colecciones: (ICMM) Artículos
(IIQ) Artículos

Mostrar el registro completo

CORE Recommender

SCOPUSTM   
Citations

5
checked on 24-mar-2024

WEB OF SCIENCETM
Citations

4
checked on 22-feb-2024

Page view(s)

418
checked on 28-mar-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.