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Abstract:

The use of tetraethyl ethylidenebis(phosphonate) as a Michael acceptor with different nucleophiles was investigated. It was found that in some cases this compound undergoes phosphate removal, depending on the nature of the nucleophile. The chemical behavior of its epoxy derivative tetraethyl oxiranylidenebis(phosphonate) as an electrophile was also studied. This compound underwent a very attractive and remarkable phosphonate-phosphate rearrangement resulting in the enol phosphate 8 regardless of the nucleophile employed. Different mechanistic studies were conducted in an attempt to explain the mechanisms involved. To the best of our knowledge, this reaction constitutes a remarkable novelty, being the first reported rearrangement reaction of an epoxy derivative of a gem-bis(phosphonate). In addition, evidence supporting the involvement of a radical or a polar mechanism, depending on the nature of the nucleophile, is discussed. © Wiley-VCH Verlag GmbH & Co. KGaA, 2005.

Registro:

Documento: Artículo
Título:New insights into the chemistry of gem-bis(phosphonates): Unexpected rearrangement of Michael-type acceptors
Autor:Szajnman, S.H.; Liñares, G.G.; Moro, P.; Rodriguez, J.B.
Filiación:Departamento de Química Orgánica, Facultad de Ciencias Exactas Y Naturales, Ciudad Universitaria, C1428EHA, Buenos Aires, Argentina
Palabras clave:Bis(phosphonic acids); Michael additions; Polar mechanism; Radical mechanism
Año:2005
Número:17
Página de inicio:3687
Página de fin:3696
DOI: http://dx.doi.org/10.1002/ejoc.200500097
Título revista:European Journal of Organic Chemistry
Título revista abreviado:Eur. J. Org. Chem.
ISSN:1434193X
CODEN:EJOCF
Registro:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_1434193X_v_n17_p3687_Szajnman

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Citas:

---------- APA ----------
Szajnman, S.H., Liñares, G.G., Moro, P. & Rodriguez, J.B. (2005) . New insights into the chemistry of gem-bis(phosphonates): Unexpected rearrangement of Michael-type acceptors. European Journal of Organic Chemistry(17), 3687-3696.
http://dx.doi.org/10.1002/ejoc.200500097
---------- CHICAGO ----------
Szajnman, S.H., Liñares, G.G., Moro, P., Rodriguez, J.B. "New insights into the chemistry of gem-bis(phosphonates): Unexpected rearrangement of Michael-type acceptors" . European Journal of Organic Chemistry, no. 17 (2005) : 3687-3696.
http://dx.doi.org/10.1002/ejoc.200500097
---------- MLA ----------
Szajnman, S.H., Liñares, G.G., Moro, P., Rodriguez, J.B. "New insights into the chemistry of gem-bis(phosphonates): Unexpected rearrangement of Michael-type acceptors" . European Journal of Organic Chemistry, no. 17, 2005, pp. 3687-3696.
http://dx.doi.org/10.1002/ejoc.200500097
---------- VANCOUVER ----------
Szajnman, S.H., Liñares, G.G., Moro, P., Rodriguez, J.B. New insights into the chemistry of gem-bis(phosphonates): Unexpected rearrangement of Michael-type acceptors. Eur. J. Org. Chem. 2005(17):3687-3696.
http://dx.doi.org/10.1002/ejoc.200500097