New insights into the chemistry of gem-bis(phosphonates): Unexpected rearrangement of Michael-type acceptors
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 oxirany...
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| Acceso en línea: | http://hdl.handle.net/20.500.12110/paper_1434193X_v_n17_p3687_Szajnman |
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todo:paper_1434193X_v_n17_p3687_Szajnman2023-10-03T16:14:16Z New insights into the chemistry of gem-bis(phosphonates): Unexpected rearrangement of Michael-type acceptors Szajnman, S.H. Liñares, G.G. Moro, P. Rodriguez, J.B. Bis(phosphonic acids) Michael additions Polar mechanism Radical mechanism 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. Fil:Szajnman, S.H. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. Fil:Rodriguez, J.B. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. JOUR info:eu-repo/semantics/openAccess http://creativecommons.org/licenses/by/2.5/ar http://hdl.handle.net/20.500.12110/paper_1434193X_v_n17_p3687_Szajnman |
| institution |
Universidad de Buenos Aires |
| institution_str |
I-28 |
| repository_str |
R-134 |
| collection |
Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) |
| topic |
Bis(phosphonic acids) Michael additions Polar mechanism Radical mechanism |
| spellingShingle |
Bis(phosphonic acids) Michael additions Polar mechanism Radical mechanism 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 |
| topic_facet |
Bis(phosphonic acids) Michael additions Polar mechanism Radical mechanism |
| description |
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. |
| format |
JOUR |
| author |
Szajnman, S.H. Liñares, G.G. Moro, P. Rodriguez, J.B. |
| author_facet |
Szajnman, S.H. Liñares, G.G. Moro, P. Rodriguez, J.B. |
| author_sort |
Szajnman, S.H. |
| title |
New insights into the chemistry of gem-bis(phosphonates): Unexpected rearrangement of Michael-type acceptors |
| title_short |
New insights into the chemistry of gem-bis(phosphonates): Unexpected rearrangement of Michael-type acceptors |
| title_full |
New insights into the chemistry of gem-bis(phosphonates): Unexpected rearrangement of Michael-type acceptors |
| title_fullStr |
New insights into the chemistry of gem-bis(phosphonates): Unexpected rearrangement of Michael-type acceptors |
| title_full_unstemmed |
New insights into the chemistry of gem-bis(phosphonates): Unexpected rearrangement of Michael-type acceptors |
| title_sort |
new insights into the chemistry of gem-bis(phosphonates): unexpected rearrangement of michael-type acceptors |
| url |
http://hdl.handle.net/20.500.12110/paper_1434193X_v_n17_p3687_Szajnman |
| work_keys_str_mv |
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