Preparation and absolute configuration of (1R,4R)-(+)-oxo-, (1S,4S)-(-)-3-oxo-and (1R,3S,4R)-(+)-3-acetyloxy-5-oxo-1,8-cineole

Autores
Loandos, Maria del Huerto; Villecco, Margarita Beatriz; Burgueño Tapia, Eleuterio; Joseph Nathan, Pedro; Catalan, Cesar Atilio Nazareno
Año de publicación
2009
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Enantiomerically pure (1S,4S)-(-)-3-oxo-1,8-cineole (-)-2 and (1R,4R)-(+)-3-oxo-1,8-cineole (+)-2 were prepared for the first time and their absolute configurations assigned by vibrational circular dichroism (VCD) measurements. Thus, treatment of cineole 1 with chromyl acetate gave rac-2 which after sodium borohydride reduction and acetylation provided racemic 3-endo-acetyloxy-1,8-cineole, rac-4. Enantioselective hydrolysis using porcine liver esterase (PLE) gave a mixture of 3-endo-hydroxy-1,8-cineole (-)-3 and 3-endo-acetyloxy-1,8-cineole (+)-4. After chromatographic separation, (-)-3 was oxidized to (+)-2, while (+)-4 was hydrolysed to (+)-3 and then oxidized to (-)-2. The absolute configuration of either ketonewas established by VCD spectroscopy in combination with density functional theory (DFT) calculations at the B3LYP/DGDZVP level of theory, from where it followed that the (+)-2 enantiomer corresponds to (1R,4R)-1,3,3-trimethyl-5-oxo-2-oxabicyclo[2.2.2]octane and the (-)-2 enantiomer to the (1S,4S) molecule which is also in agreement with the absolute configuration deduced by the Mosher method for the starting chiral alcohols. Some literature inconsistencies are clarified. In addition, the enantiomerically pure monoester (1S,3S,4R,5R)-(-)-3-acetyloxy-5-hydroxy-1,8-cineole 6 and the ketoester (1R,3S,4R)-(+)-3-acetyloxy-5-oxo-1,8-cineole 7 were prepared from meso-diacetate 5 by enantioselective asymmetrization also using PLE.
Fil: Loandos, Maria del Huerto. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tucumán. Instituto de Química del Noroeste. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química del Noroeste; Argentina
Fil: Villecco, Margarita Beatriz. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tucumán. Instituto de Química del Noroeste. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química del Noroeste; Argentina
Fil: Burgueño Tapia, Eleuterio. Instituto Politécnico Nacional; México
Fil: Joseph Nathan, Pedro. Instituto Politécnico Nacional; México
Fil: Catalan, Cesar Atilio Nazareno. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tucumán. Instituto de Química del Noroeste. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química del Noroeste; Argentina
Materia
Acetyloxy
Cineole
Pharmacology
Hydrolysed
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by-nc/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/59419
Acceder
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repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Preparation and absolute configuration of (1R,4R)-(+)-oxo-, (1S,4S)-(-)-3-oxo-and (1R,3S,4R)-(+)-3-acetyloxy-5-oxo-1,8-cineoleLoandos, Maria del HuertoVillecco, Margarita BeatrizBurgueño Tapia, EleuterioJoseph Nathan, PedroCatalan, Cesar Atilio NazarenoAcetyloxyCineolePharmacologyHydrolysedhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1Enantiomerically pure (1S,4S)-(-)-3-oxo-1,8-cineole (-)-2 and (1R,4R)-(+)-3-oxo-1,8-cineole (+)-2 were prepared for the first time and their absolute configurations assigned by vibrational circular dichroism (VCD) measurements. Thus, treatment of cineole 1 with chromyl acetate gave rac-2 which after sodium borohydride reduction and acetylation provided racemic 3-endo-acetyloxy-1,8-cineole, rac-4. Enantioselective hydrolysis using porcine liver esterase (PLE) gave a mixture of 3-endo-hydroxy-1,8-cineole (-)-3 and 3-endo-acetyloxy-1,8-cineole (+)-4. After chromatographic separation, (-)-3 was oxidized to (+)-2, while (+)-4 was hydrolysed to (+)-3 and then oxidized to (-)-2. The absolute configuration of either ketonewas established by VCD spectroscopy in combination with density functional theory (DFT) calculations at the B3LYP/DGDZVP level of theory, from where it followed that the (+)-2 enantiomer corresponds to (1R,4R)-1,3,3-trimethyl-5-oxo-2-oxabicyclo[2.2.2]octane and the (-)-2 enantiomer to the (1S,4S) molecule which is also in agreement with the absolute configuration deduced by the Mosher method for the starting chiral alcohols. Some literature inconsistencies are clarified. In addition, the enantiomerically pure monoester (1S,3S,4R,5R)-(-)-3-acetyloxy-5-hydroxy-1,8-cineole 6 and the ketoester (1R,3S,4R)-(+)-3-acetyloxy-5-oxo-1,8-cineole 7 were prepared from meso-diacetate 5 by enantioselective asymmetrization also using PLE.Fil: Loandos, Maria del Huerto. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tucumán. Instituto de Química del Noroeste. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química del Noroeste; ArgentinaFil: Villecco, Margarita Beatriz. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tucumán. Instituto de Química del Noroeste. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química del Noroeste; ArgentinaFil: Burgueño Tapia, Eleuterio. Instituto Politécnico Nacional; MéxicoFil: Joseph Nathan, Pedro. Instituto Politécnico Nacional; MéxicoFil: Catalan, Cesar Atilio Nazareno. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tucumán. Instituto de Química del Noroeste. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química del Noroeste; ArgentinaNatural Products2009-11info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/59419Loandos, Maria del Huerto; Villecco, Margarita Beatriz; Burgueño Tapia, Eleuterio; Joseph Nathan, Pedro; Catalan, Cesar Atilio Nazareno; Preparation and absolute configuration of (1R,4R)-(+)-oxo-, (1S,4S)-(-)-3-oxo-and (1R,3S,4R)-(+)-3-acetyloxy-5-oxo-1,8-cineole; Natural Products; Natural Product Communications; 4; 11; 11-2009; 1537-15451934-578XCONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://journals.sagepub.com/doi/abs/10.1177/1934578X0900401116info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-03T10:03:39Zoai:ri.conicet.gov.ar:11336/59419instacron: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:34982025-09-03 10:03:39.791CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Preparation and absolute configuration of (1R,4R)-(+)-oxo-, (1S,4S)-(-)-3-oxo-and (1R,3S,4R)-(+)-3-acetyloxy-5-oxo-1,8-cineole
title Preparation and absolute configuration of (1R,4R)-(+)-oxo-, (1S,4S)-(-)-3-oxo-and (1R,3S,4R)-(+)-3-acetyloxy-5-oxo-1,8-cineole
spellingShingle Preparation and absolute configuration of (1R,4R)-(+)-oxo-, (1S,4S)-(-)-3-oxo-and (1R,3S,4R)-(+)-3-acetyloxy-5-oxo-1,8-cineole
Loandos, Maria del Huerto
Acetyloxy
Cineole
Pharmacology
Hydrolysed
title_short Preparation and absolute configuration of (1R,4R)-(+)-oxo-, (1S,4S)-(-)-3-oxo-and (1R,3S,4R)-(+)-3-acetyloxy-5-oxo-1,8-cineole
title_full Preparation and absolute configuration of (1R,4R)-(+)-oxo-, (1S,4S)-(-)-3-oxo-and (1R,3S,4R)-(+)-3-acetyloxy-5-oxo-1,8-cineole
title_fullStr Preparation and absolute configuration of (1R,4R)-(+)-oxo-, (1S,4S)-(-)-3-oxo-and (1R,3S,4R)-(+)-3-acetyloxy-5-oxo-1,8-cineole
title_full_unstemmed Preparation and absolute configuration of (1R,4R)-(+)-oxo-, (1S,4S)-(-)-3-oxo-and (1R,3S,4R)-(+)-3-acetyloxy-5-oxo-1,8-cineole
title_sort Preparation and absolute configuration of (1R,4R)-(+)-oxo-, (1S,4S)-(-)-3-oxo-and (1R,3S,4R)-(+)-3-acetyloxy-5-oxo-1,8-cineole
dc.creator.none.fl_str_mv Loandos, Maria del Huerto
Villecco, Margarita Beatriz
Burgueño Tapia, Eleuterio
Joseph Nathan, Pedro
Catalan, Cesar Atilio Nazareno
author Loandos, Maria del Huerto
author_facet Loandos, Maria del Huerto
Villecco, Margarita Beatriz
Burgueño Tapia, Eleuterio
Joseph Nathan, Pedro
Catalan, Cesar Atilio Nazareno
author_role author
author2 Villecco, Margarita Beatriz
Burgueño Tapia, Eleuterio
Joseph Nathan, Pedro
Catalan, Cesar Atilio Nazareno
author2_role author
author
author
author
dc.subject.none.fl_str_mv Acetyloxy
Cineole
Pharmacology
Hydrolysed
topic Acetyloxy
Cineole
Pharmacology
Hydrolysed
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv Enantiomerically pure (1S,4S)-(-)-3-oxo-1,8-cineole (-)-2 and (1R,4R)-(+)-3-oxo-1,8-cineole (+)-2 were prepared for the first time and their absolute configurations assigned by vibrational circular dichroism (VCD) measurements. Thus, treatment of cineole 1 with chromyl acetate gave rac-2 which after sodium borohydride reduction and acetylation provided racemic 3-endo-acetyloxy-1,8-cineole, rac-4. Enantioselective hydrolysis using porcine liver esterase (PLE) gave a mixture of 3-endo-hydroxy-1,8-cineole (-)-3 and 3-endo-acetyloxy-1,8-cineole (+)-4. After chromatographic separation, (-)-3 was oxidized to (+)-2, while (+)-4 was hydrolysed to (+)-3 and then oxidized to (-)-2. The absolute configuration of either ketonewas established by VCD spectroscopy in combination with density functional theory (DFT) calculations at the B3LYP/DGDZVP level of theory, from where it followed that the (+)-2 enantiomer corresponds to (1R,4R)-1,3,3-trimethyl-5-oxo-2-oxabicyclo[2.2.2]octane and the (-)-2 enantiomer to the (1S,4S) molecule which is also in agreement with the absolute configuration deduced by the Mosher method for the starting chiral alcohols. Some literature inconsistencies are clarified. In addition, the enantiomerically pure monoester (1S,3S,4R,5R)-(-)-3-acetyloxy-5-hydroxy-1,8-cineole 6 and the ketoester (1R,3S,4R)-(+)-3-acetyloxy-5-oxo-1,8-cineole 7 were prepared from meso-diacetate 5 by enantioselective asymmetrization also using PLE.
Fil: Loandos, Maria del Huerto. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tucumán. Instituto de Química del Noroeste. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química del Noroeste; Argentina
Fil: Villecco, Margarita Beatriz. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tucumán. Instituto de Química del Noroeste. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química del Noroeste; Argentina
Fil: Burgueño Tapia, Eleuterio. Instituto Politécnico Nacional; México
Fil: Joseph Nathan, Pedro. Instituto Politécnico Nacional; México
Fil: Catalan, Cesar Atilio Nazareno. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tucumán. Instituto de Química del Noroeste. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química del Noroeste; Argentina
description Enantiomerically pure (1S,4S)-(-)-3-oxo-1,8-cineole (-)-2 and (1R,4R)-(+)-3-oxo-1,8-cineole (+)-2 were prepared for the first time and their absolute configurations assigned by vibrational circular dichroism (VCD) measurements. Thus, treatment of cineole 1 with chromyl acetate gave rac-2 which after sodium borohydride reduction and acetylation provided racemic 3-endo-acetyloxy-1,8-cineole, rac-4. Enantioselective hydrolysis using porcine liver esterase (PLE) gave a mixture of 3-endo-hydroxy-1,8-cineole (-)-3 and 3-endo-acetyloxy-1,8-cineole (+)-4. After chromatographic separation, (-)-3 was oxidized to (+)-2, while (+)-4 was hydrolysed to (+)-3 and then oxidized to (-)-2. The absolute configuration of either ketonewas established by VCD spectroscopy in combination with density functional theory (DFT) calculations at the B3LYP/DGDZVP level of theory, from where it followed that the (+)-2 enantiomer corresponds to (1R,4R)-1,3,3-trimethyl-5-oxo-2-oxabicyclo[2.2.2]octane and the (-)-2 enantiomer to the (1S,4S) molecule which is also in agreement with the absolute configuration deduced by the Mosher method for the starting chiral alcohols. Some literature inconsistencies are clarified. In addition, the enantiomerically pure monoester (1S,3S,4R,5R)-(-)-3-acetyloxy-5-hydroxy-1,8-cineole 6 and the ketoester (1R,3S,4R)-(+)-3-acetyloxy-5-oxo-1,8-cineole 7 were prepared from meso-diacetate 5 by enantioselective asymmetrization also using PLE.
publishDate 2009
dc.date.none.fl_str_mv 2009-11
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/11336/59419
Loandos, Maria del Huerto; Villecco, Margarita Beatriz; Burgueño Tapia, Eleuterio; Joseph Nathan, Pedro; Catalan, Cesar Atilio Nazareno; Preparation and absolute configuration of (1R,4R)-(+)-oxo-, (1S,4S)-(-)-3-oxo-and (1R,3S,4R)-(+)-3-acetyloxy-5-oxo-1,8-cineole; Natural Products; Natural Product Communications; 4; 11; 11-2009; 1537-1545
1934-578X
CONICET Digital
CONICET
url http://hdl.handle.net/11336/59419
identifier_str_mv Loandos, Maria del Huerto; Villecco, Margarita Beatriz; Burgueño Tapia, Eleuterio; Joseph Nathan, Pedro; Catalan, Cesar Atilio Nazareno; Preparation and absolute configuration of (1R,4R)-(+)-oxo-, (1S,4S)-(-)-3-oxo-and (1R,3S,4R)-(+)-3-acetyloxy-5-oxo-1,8-cineole; Natural Products; Natural Product Communications; 4; 11; 11-2009; 1537-1545
1934-578X
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://journals.sagepub.com/doi/abs/10.1177/1934578X0900401116
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by-nc/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by-nc/2.5/ar/
dc.format.none.fl_str_mv application/pdf
application/pdf
application/pdf
application/pdf
dc.publisher.none.fl_str_mv Natural Products
publisher.none.fl_str_mv Natural Products
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_ 1842269812672167936
score 13.13397

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