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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Autores principales:	Szajnman, Sergio Hernán, Rodríguez, Juan Bautista
Publicado:	2005
Materias:	Bis(phosphonic acids) Michael additions Polar mechanism Radical mechanism
Acceso en línea:	https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_1434193X_v_n17_p3687_Szajnman http://hdl.handle.net/20.500.12110/paper_1434193X_v_n17_p3687_Szajnman
Aporte de:	Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) de Universidad de Buenos Aires

id	paper:paper_1434193X_v_n17_p3687_Szajnman
record_format	dspace
spelling	paper:paper_1434193X_v_n17_p3687_Szajnman2023-06-08T16:14:23Z New insights into the chemistry of gem-bis(phosphonates): Unexpected rearrangement of Michael-type acceptors Szajnman, Sergio Hernán Rodríguez, Juan Bautista 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. 2005 https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_1434193X_v_n17_p3687_Szajnman 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, Sergio Hernán Rodríguez, Juan Bautista 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.
author	Szajnman, Sergio Hernán Rodríguez, Juan Bautista
author_facet	Szajnman, Sergio Hernán Rodríguez, Juan Bautista
author_sort	Szajnman, Sergio Hernán
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
publishDate	2005
url	https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_1434193X_v_n17_p3687_Szajnman http://hdl.handle.net/20.500.12110/paper_1434193X_v_n17_p3687_Szajnman
work_keys_str_mv	AT szajnmansergiohernan newinsightsintothechemistryofgembisphosphonatesunexpectedrearrangementofmichaeltypeacceptors AT rodriguezjuanbautista newinsightsintothechemistryofgembisphosphonatesunexpectedrearrangementofmichaeltypeacceptors
_version_	1768545109258797056

New insights into the chemistry of gem-bis(phosphonates): Unexpected rearrangement of Michael-type acceptors

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