Synthetic and computational studies on the tricarboxylate core of 6,7-dideoxysqualestatin H5 involving a carbonyl ylide cycloaddition- rearrangement

Autores
Hodgson, David M.; Villalonga-Barber, Carolina; Goodman, Jonathan M.; Pellegrinet, Silvina Carla
Año de publicación
2010
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Reaction of diazodiketoesters 17 and 28 with methyl glyoxylate in the presence of catalytic rhodium(ii) acetate generates predominantly the 6,8-dioxabicyclo[3.2.1]octanes 29 and 30, respectively. Acid-catalysed rearrangement of the corresponding alcohol 31 favours, at equilibrium, the 2,8-dioxabicyclo[3.2.1]octane skeleton 33 of the squalestatins-zaragozic acids. Force field calculations on the position of the equilibrium gave misleading results. DFT calculations were correct in suggesting that the energy difference between 31 and 33 should be small, but did not always suggest the right major product. Calculation of the NMR spectra of the similar structures could be used to assign the isomers with a high level of confidence.
Fil: Hodgson, David M.. University of Oxford; Reino Unido
Fil: Villalonga-Barber, Carolina. National Hellenic Research Foundation; Grecia
Fil: Goodman, Jonathan M.. Unilever Centre for Molecular Science Informatics; Reino Unido
Fil: Pellegrinet, Silvina Carla. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina
Materia
squalestatinszaragozic acids
cycloaddition
Acid-catalysed rearrangement
theoretical calculations
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/129512
Acceder
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network_name_str CONICET Digital (CONICET)
spelling Synthetic and computational studies on the tricarboxylate core of 6,7-dideoxysqualestatin H5 involving a carbonyl ylide cycloaddition- rearrangementHodgson, David M.Villalonga-Barber, CarolinaGoodman, Jonathan M.Pellegrinet, Silvina Carlasqualestatinszaragozic acidscycloadditionAcid-catalysed rearrangementtheoretical calculationshttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1Reaction of diazodiketoesters 17 and 28 with methyl glyoxylate in the presence of catalytic rhodium(ii) acetate generates predominantly the 6,8-dioxabicyclo[3.2.1]octanes 29 and 30, respectively. Acid-catalysed rearrangement of the corresponding alcohol 31 favours, at equilibrium, the 2,8-dioxabicyclo[3.2.1]octane skeleton 33 of the squalestatins-zaragozic acids. Force field calculations on the position of the equilibrium gave misleading results. DFT calculations were correct in suggesting that the energy difference between 31 and 33 should be small, but did not always suggest the right major product. Calculation of the NMR spectra of the similar structures could be used to assign the isomers with a high level of confidence.Fil: Hodgson, David M.. University of Oxford; Reino UnidoFil: Villalonga-Barber, Carolina. National Hellenic Research Foundation; GreciaFil: Goodman, Jonathan M.. Unilever Centre for Molecular Science Informatics; Reino UnidoFil: Pellegrinet, Silvina Carla. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; ArgentinaRoyal Society of Chemistry2010-07info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/129512Hodgson, David M.; Villalonga-Barber, Carolina; Goodman, Jonathan M.; Pellegrinet, Silvina Carla; Synthetic and computational studies on the tricarboxylate core of 6,7-dideoxysqualestatin H5 involving a carbonyl ylide cycloaddition- rearrangement; Royal Society of Chemistry; Organic & Biomolecular Chemistry; 8; 17; 7-2010; 3975-39841477-0520CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://pubs.rsc.org/en/content/articlelanding/2010/OB/c004496b#!divAbstractinfo:eu-repo/semantics/altIdentifier/doi/10.1039/C004496Binfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-10-22T12:13:43Zoai:ri.conicet.gov.ar:11336/129512instacron:CONICETInstitucionalhttp://ri.conicet.gov.ar/Organismo científico-tecnológicoNo correspondehttp://ri.conicet.gov.ar/oai/requestdasensio@conicet.gov.ar; lcarlino@conicet.gov.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:34982025-10-22 12:13:43.912CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Synthetic and computational studies on the tricarboxylate core of 6,7-dideoxysqualestatin H5 involving a carbonyl ylide cycloaddition- rearrangement
title Synthetic and computational studies on the tricarboxylate core of 6,7-dideoxysqualestatin H5 involving a carbonyl ylide cycloaddition- rearrangement
spellingShingle Synthetic and computational studies on the tricarboxylate core of 6,7-dideoxysqualestatin H5 involving a carbonyl ylide cycloaddition- rearrangement
Hodgson, David M.
squalestatinszaragozic acids
cycloaddition
Acid-catalysed rearrangement
theoretical calculations
title_short Synthetic and computational studies on the tricarboxylate core of 6,7-dideoxysqualestatin H5 involving a carbonyl ylide cycloaddition- rearrangement
title_full Synthetic and computational studies on the tricarboxylate core of 6,7-dideoxysqualestatin H5 involving a carbonyl ylide cycloaddition- rearrangement
title_fullStr Synthetic and computational studies on the tricarboxylate core of 6,7-dideoxysqualestatin H5 involving a carbonyl ylide cycloaddition- rearrangement
title_full_unstemmed Synthetic and computational studies on the tricarboxylate core of 6,7-dideoxysqualestatin H5 involving a carbonyl ylide cycloaddition- rearrangement
title_sort Synthetic and computational studies on the tricarboxylate core of 6,7-dideoxysqualestatin H5 involving a carbonyl ylide cycloaddition- rearrangement
dc.creator.none.fl_str_mv Hodgson, David M.
Villalonga-Barber, Carolina
Goodman, Jonathan M.
Pellegrinet, Silvina Carla
author Hodgson, David M.
author_facet Hodgson, David M.
Villalonga-Barber, Carolina
Goodman, Jonathan M.
Pellegrinet, Silvina Carla
author_role author
author2 Villalonga-Barber, Carolina
Goodman, Jonathan M.
Pellegrinet, Silvina Carla
author2_role author
author
author
dc.subject.none.fl_str_mv squalestatinszaragozic acids
cycloaddition
Acid-catalysed rearrangement
theoretical calculations
topic squalestatinszaragozic acids
cycloaddition
Acid-catalysed rearrangement
theoretical calculations
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv Reaction of diazodiketoesters 17 and 28 with methyl glyoxylate in the presence of catalytic rhodium(ii) acetate generates predominantly the 6,8-dioxabicyclo[3.2.1]octanes 29 and 30, respectively. Acid-catalysed rearrangement of the corresponding alcohol 31 favours, at equilibrium, the 2,8-dioxabicyclo[3.2.1]octane skeleton 33 of the squalestatins-zaragozic acids. Force field calculations on the position of the equilibrium gave misleading results. DFT calculations were correct in suggesting that the energy difference between 31 and 33 should be small, but did not always suggest the right major product. Calculation of the NMR spectra of the similar structures could be used to assign the isomers with a high level of confidence.
Fil: Hodgson, David M.. University of Oxford; Reino Unido
Fil: Villalonga-Barber, Carolina. National Hellenic Research Foundation; Grecia
Fil: Goodman, Jonathan M.. Unilever Centre for Molecular Science Informatics; Reino Unido
Fil: Pellegrinet, Silvina Carla. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina
description Reaction of diazodiketoesters 17 and 28 with methyl glyoxylate in the presence of catalytic rhodium(ii) acetate generates predominantly the 6,8-dioxabicyclo[3.2.1]octanes 29 and 30, respectively. Acid-catalysed rearrangement of the corresponding alcohol 31 favours, at equilibrium, the 2,8-dioxabicyclo[3.2.1]octane skeleton 33 of the squalestatins-zaragozic acids. Force field calculations on the position of the equilibrium gave misleading results. DFT calculations were correct in suggesting that the energy difference between 31 and 33 should be small, but did not always suggest the right major product. Calculation of the NMR spectra of the similar structures could be used to assign the isomers with a high level of confidence.
publishDate 2010
dc.date.none.fl_str_mv 2010-07
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
http://purl.org/coar/resource_type/c_6501
info:ar-repo/semantics/articulo
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/11336/129512
Hodgson, David M.; Villalonga-Barber, Carolina; Goodman, Jonathan M.; Pellegrinet, Silvina Carla; Synthetic and computational studies on the tricarboxylate core of 6,7-dideoxysqualestatin H5 involving a carbonyl ylide cycloaddition- rearrangement; Royal Society of Chemistry; Organic & Biomolecular Chemistry; 8; 17; 7-2010; 3975-3984
1477-0520
CONICET Digital
CONICET
url http://hdl.handle.net/11336/129512
identifier_str_mv Hodgson, David M.; Villalonga-Barber, Carolina; Goodman, Jonathan M.; Pellegrinet, Silvina Carla; Synthetic and computational studies on the tricarboxylate core of 6,7-dideoxysqualestatin H5 involving a carbonyl ylide cycloaddition- rearrangement; Royal Society of Chemistry; Organic & Biomolecular Chemistry; 8; 17; 7-2010; 3975-3984
1477-0520
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/https://pubs.rsc.org/en/content/articlelanding/2010/OB/c004496b#!divAbstract
info:eu-repo/semantics/altIdentifier/doi/10.1039/C004496B
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
dc.format.none.fl_str_mv application/pdf
application/pdf
dc.publisher.none.fl_str_mv Royal Society of Chemistry
publisher.none.fl_str_mv Royal Society of Chemistry
dc.source.none.fl_str_mv reponame:CONICET Digital (CONICET)
instname:Consejo Nacional de Investigaciones Científicas y Técnicas
reponame_str CONICET Digital (CONICET)
collection CONICET Digital (CONICET)
instname_str Consejo Nacional de Investigaciones Científicas y Técnicas
repository.name.fl_str_mv CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicas
repository.mail.fl_str_mv dasensio@conicet.gov.ar; lcarlino@conicet.gov.ar
_version_ 1846782540928516096
score 12.982451

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