Structure Elucidation and Absolute Stereochemistry of Isomeric Monoterpene Chromane Esters

Autores
Batista Junior, João Marcos; De Luca Batista, Andrea Nastri; Da Silva Mota, Jonas; Cass,Quezia Bezerra; Kato, Massuo Jorge; da Silva Bolzani, Vanderlan; Freedman, Teresa B.; López, Silvia Noelí; Furlan, Maysa; Nafie, L.A.
Año de publicación
2011
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Six novel monoterpene chromane esters were isolated from the aerial parts of Peperomia obtusifolia (Piperaceae) using chiral chromatography. This is the first time that chiral chromane esters of this kind, ones with a tethered chiral terpene, have been isolated in nature. Due to theirstructural features, it is not currently possible to assess directly their absolute stereochemistry using any of the standard classical approaches, such as X-ray crystallography, NMR, optical rotation, or electronic circular dichroism (ECD). Herein we report the absolute configuration of these molecules, involving four chiral centers, using vibrational circular dichroism (VCD) and density functional theory (DFT) (B3LYP/6-31G*) calculations. This work further reinforces the capability of VCD to determine unambiguously the absolute configuration of structurally complex molecules in solution, without crystallization or derivatization, and demonstrates the sensitivity of VCD to specify the absolute configuration for just one among a number of chiral centers. We also demonstrate the sufficiency of using the so-called inexpensive basis set 6-31G* compared to the triple-ζ basis set TZVP for absolute configuration analysis of larger molecules using VCD. Overall, this work extends our knowledge of secondary metabolites in plants and provides a straightforward way to determine the absolute configuration of complex natural products involving a chiral parent moiety combined with a chiral terpene adduct.
Fil: Batista Junior, João Marcos. Universidade Estadual Paulista Julio de Mesquita Filho; Brasil
Fil: De Luca Batista, Andrea Nastri. Universidade Estadual Paulista Julio de Mesquita Filho; Brasil
Fil: Da Silva Mota, Jonas. Universidade Estadual Paulista Julio de Mesquita Filho; Brasil
Fil: Cass,Quezia Bezerra. Universidade Estadual Paulista Julio de Mesquita Filho; Brasil
Fil: Kato, Massuo Jorge. Universidade Estadual Paulista Julio de Mesquita Filho; Brasil
Fil: da Silva Bolzani, Vanderlan. Universidade Estadual Paulista Julio de Mesquita Filho; Brasil
Fil: Freedman, Teresa B.. Syracuse University; Estados Unidos
Fil: López, Silvia Noelí. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario; Argentina. Universidade Estadual Paulista Julio de Mesquita Filho; Brasil
Fil: Furlan, Maysa. Universidade Estadual Paulista Julio de Mesquita Filho; Brasil
Fil: Nafie, L.A.. Syracuse University; Estados Unidos
Materia
ABSOLUTE CONFIGURATION
PEPEROMIA OBTUSIFOLIA
CHROMANE
VCD
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:11336/268273
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/268273
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Structure Elucidation and Absolute Stereochemistry of Isomeric Monoterpene Chromane EstersBatista Junior, João MarcosDe Luca Batista, Andrea NastriDa Silva Mota, JonasCass,Quezia BezerraKato, Massuo Jorgeda Silva Bolzani, VanderlanFreedman, Teresa B.López, Silvia NoelíFurlan, MaysaNafie, L.A.ABSOLUTE CONFIGURATIONPEPEROMIA OBTUSIFOLIACHROMANEVCDhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1Six novel monoterpene chromane esters were isolated from the aerial parts of Peperomia obtusifolia (Piperaceae) using chiral chromatography. This is the first time that chiral chromane esters of this kind, ones with a tethered chiral terpene, have been isolated in nature. Due to theirstructural features, it is not currently possible to assess directly their absolute stereochemistry using any of the standard classical approaches, such as X-ray crystallography, NMR, optical rotation, or electronic circular dichroism (ECD). Herein we report the absolute configuration of these molecules, involving four chiral centers, using vibrational circular dichroism (VCD) and density functional theory (DFT) (B3LYP/6-31G*) calculations. This work further reinforces the capability of VCD to determine unambiguously the absolute configuration of structurally complex molecules in solution, without crystallization or derivatization, and demonstrates the sensitivity of VCD to specify the absolute configuration for just one among a number of chiral centers. We also demonstrate the sufficiency of using the so-called inexpensive basis set 6-31G* compared to the triple-ζ basis set TZVP for absolute configuration analysis of larger molecules using VCD. Overall, this work extends our knowledge of secondary metabolites in plants and provides a straightforward way to determine the absolute configuration of complex natural products involving a chiral parent moiety combined with a chiral terpene adduct.Fil: Batista Junior, João Marcos. Universidade Estadual Paulista Julio de Mesquita Filho; BrasilFil: De Luca Batista, Andrea Nastri. Universidade Estadual Paulista Julio de Mesquita Filho; BrasilFil: Da Silva Mota, Jonas. Universidade Estadual Paulista Julio de Mesquita Filho; BrasilFil: Cass,Quezia Bezerra. Universidade Estadual Paulista Julio de Mesquita Filho; BrasilFil: Kato, Massuo Jorge. Universidade Estadual Paulista Julio de Mesquita Filho; BrasilFil: da Silva Bolzani, Vanderlan. Universidade Estadual Paulista Julio de Mesquita Filho; BrasilFil: Freedman, Teresa B.. Syracuse University; Estados UnidosFil: López, Silvia Noelí. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario; Argentina. Universidade Estadual Paulista Julio de Mesquita Filho; BrasilFil: Furlan, Maysa. Universidade Estadual Paulista Julio de Mesquita Filho; BrasilFil: Nafie, L.A.. Syracuse University; Estados UnidosAmerican Chemical Society2011-04info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/268273Batista Junior, João Marcos; De Luca Batista, Andrea Nastri; Da Silva Mota, Jonas; Cass,Quezia Bezerra; Kato, Massuo Jorge; et al.; Structure Elucidation and Absolute Stereochemistry of Isomeric Monoterpene Chromane Esters; American Chemical Society; Journal of Organic Chemistry; 76; 8; 4-2011; 2603-26120022-3263CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/http://pubs.acs.org/doi/pdf/10.1021/jo1025089info:eu-repo/semantics/altIdentifier/doi/10.1021/jo1025089info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T09:48:19Zoai:ri.conicet.gov.ar:11336/268273instacron: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:34982025-09-29 09:48:19.553CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Structure Elucidation and Absolute Stereochemistry of Isomeric Monoterpene Chromane Esters
title Structure Elucidation and Absolute Stereochemistry of Isomeric Monoterpene Chromane Esters
spellingShingle Structure Elucidation and Absolute Stereochemistry of Isomeric Monoterpene Chromane Esters
Batista Junior, João Marcos
ABSOLUTE CONFIGURATION
PEPEROMIA OBTUSIFOLIA
CHROMANE
VCD
title_short Structure Elucidation and Absolute Stereochemistry of Isomeric Monoterpene Chromane Esters
title_full Structure Elucidation and Absolute Stereochemistry of Isomeric Monoterpene Chromane Esters
title_fullStr Structure Elucidation and Absolute Stereochemistry of Isomeric Monoterpene Chromane Esters
title_full_unstemmed Structure Elucidation and Absolute Stereochemistry of Isomeric Monoterpene Chromane Esters
title_sort Structure Elucidation and Absolute Stereochemistry of Isomeric Monoterpene Chromane Esters
dc.creator.none.fl_str_mv Batista Junior, João Marcos
De Luca Batista, Andrea Nastri
Da Silva Mota, Jonas
Cass,Quezia Bezerra
Kato, Massuo Jorge
da Silva Bolzani, Vanderlan
Freedman, Teresa B.
López, Silvia Noelí
Furlan, Maysa
Nafie, L.A.
author Batista Junior, João Marcos
author_facet Batista Junior, João Marcos
De Luca Batista, Andrea Nastri
Da Silva Mota, Jonas
Cass,Quezia Bezerra
Kato, Massuo Jorge
da Silva Bolzani, Vanderlan
Freedman, Teresa B.
López, Silvia Noelí
Furlan, Maysa
Nafie, L.A.
author_role author
author2 De Luca Batista, Andrea Nastri
Da Silva Mota, Jonas
Cass,Quezia Bezerra
Kato, Massuo Jorge
da Silva Bolzani, Vanderlan
Freedman, Teresa B.
López, Silvia Noelí
Furlan, Maysa
Nafie, L.A.
author2_role author
author
author
author
author
author
author
author
author
dc.subject.none.fl_str_mv ABSOLUTE CONFIGURATION
PEPEROMIA OBTUSIFOLIA
CHROMANE
VCD
topic ABSOLUTE CONFIGURATION
PEPEROMIA OBTUSIFOLIA
CHROMANE
VCD
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv Six novel monoterpene chromane esters were isolated from the aerial parts of Peperomia obtusifolia (Piperaceae) using chiral chromatography. This is the first time that chiral chromane esters of this kind, ones with a tethered chiral terpene, have been isolated in nature. Due to theirstructural features, it is not currently possible to assess directly their absolute stereochemistry using any of the standard classical approaches, such as X-ray crystallography, NMR, optical rotation, or electronic circular dichroism (ECD). Herein we report the absolute configuration of these molecules, involving four chiral centers, using vibrational circular dichroism (VCD) and density functional theory (DFT) (B3LYP/6-31G*) calculations. This work further reinforces the capability of VCD to determine unambiguously the absolute configuration of structurally complex molecules in solution, without crystallization or derivatization, and demonstrates the sensitivity of VCD to specify the absolute configuration for just one among a number of chiral centers. We also demonstrate the sufficiency of using the so-called inexpensive basis set 6-31G* compared to the triple-ζ basis set TZVP for absolute configuration analysis of larger molecules using VCD. Overall, this work extends our knowledge of secondary metabolites in plants and provides a straightforward way to determine the absolute configuration of complex natural products involving a chiral parent moiety combined with a chiral terpene adduct.
Fil: Batista Junior, João Marcos. Universidade Estadual Paulista Julio de Mesquita Filho; Brasil
Fil: De Luca Batista, Andrea Nastri. Universidade Estadual Paulista Julio de Mesquita Filho; Brasil
Fil: Da Silva Mota, Jonas. Universidade Estadual Paulista Julio de Mesquita Filho; Brasil
Fil: Cass,Quezia Bezerra. Universidade Estadual Paulista Julio de Mesquita Filho; Brasil
Fil: Kato, Massuo Jorge. Universidade Estadual Paulista Julio de Mesquita Filho; Brasil
Fil: da Silva Bolzani, Vanderlan. Universidade Estadual Paulista Julio de Mesquita Filho; Brasil
Fil: Freedman, Teresa B.. Syracuse University; Estados Unidos
Fil: López, Silvia Noelí. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario; Argentina. Universidade Estadual Paulista Julio de Mesquita Filho; Brasil
Fil: Furlan, Maysa. Universidade Estadual Paulista Julio de Mesquita Filho; Brasil
Fil: Nafie, L.A.. Syracuse University; Estados Unidos
description Six novel monoterpene chromane esters were isolated from the aerial parts of Peperomia obtusifolia (Piperaceae) using chiral chromatography. This is the first time that chiral chromane esters of this kind, ones with a tethered chiral terpene, have been isolated in nature. Due to theirstructural features, it is not currently possible to assess directly their absolute stereochemistry using any of the standard classical approaches, such as X-ray crystallography, NMR, optical rotation, or electronic circular dichroism (ECD). Herein we report the absolute configuration of these molecules, involving four chiral centers, using vibrational circular dichroism (VCD) and density functional theory (DFT) (B3LYP/6-31G*) calculations. This work further reinforces the capability of VCD to determine unambiguously the absolute configuration of structurally complex molecules in solution, without crystallization or derivatization, and demonstrates the sensitivity of VCD to specify the absolute configuration for just one among a number of chiral centers. We also demonstrate the sufficiency of using the so-called inexpensive basis set 6-31G* compared to the triple-ζ basis set TZVP for absolute configuration analysis of larger molecules using VCD. Overall, this work extends our knowledge of secondary metabolites in plants and provides a straightforward way to determine the absolute configuration of complex natural products involving a chiral parent moiety combined with a chiral terpene adduct.
publishDate 2011
dc.date.none.fl_str_mv 2011-04
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/11336/268273
Batista Junior, João Marcos; De Luca Batista, Andrea Nastri; Da Silva Mota, Jonas; Cass,Quezia Bezerra; Kato, Massuo Jorge; et al.; Structure Elucidation and Absolute Stereochemistry of Isomeric Monoterpene Chromane Esters; American Chemical Society; Journal of Organic Chemistry; 76; 8; 4-2011; 2603-2612
0022-3263
CONICET Digital
CONICET
url http://hdl.handle.net/11336/268273
identifier_str_mv Batista Junior, João Marcos; De Luca Batista, Andrea Nastri; Da Silva Mota, Jonas; Cass,Quezia Bezerra; Kato, Massuo Jorge; et al.; Structure Elucidation and Absolute Stereochemistry of Isomeric Monoterpene Chromane Esters; American Chemical Society; Journal of Organic Chemistry; 76; 8; 4-2011; 2603-2612
0022-3263
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/http://pubs.acs.org/doi/pdf/10.1021/jo1025089
info:eu-repo/semantics/altIdentifier/doi/10.1021/jo1025089
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 American Chemical Society
publisher.none.fl_str_mv American Chemical Society
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
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score 13.070432

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