First total synthesis of the only known 2-isopropyliden-2: H -benzofuran-3-one isolated from V. luetzelburgii

Autores
Pergomet, Jorgelina Leonor; Larghi, Enrique Leandro; Kaufman, Teodoro Saul; Bracca, Andrea Beatriz Juana
Año de publicación
2017
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The first total synthesis of 5-(1-hydroxy-1-ethyl)-2-isopropyliden-2H-benzofuran-3-one, is reported in its racemic and in one of its optically active [(S)-(-)] forms. This heterocycle, isolated from Verbesina luetzelburgii, is the only known 2-isopropyliden-2H-benzofuran-3-one produced by species of Verbesina. The sequence took place in eight steps and 19% overall yield (up to 33% for the chiral form), from 4′-hydroxyacetophenone. It entailed carbonyl group protection as the 1,3-dioxolane and a phenol ortho formylation, followed by a Williamson etherification with chloroacetone and an organocatalytic cross-aldolization, to afford a 2-acetyl-2,3-dihydrobenzofuran-3-ol intermediate. The latter underwent a methyl Grignard addition to the carbonyl moiety, followed by selective oxidation of the benzylic alcohol and deprotection, resulting in a β-hydroxy diketone derivative. A MsCl-assisted dehydration of the tertiary alcohol, established the isopropylidene motif, whereas the syntheses culminated by chemical or enzymatic (carrot, celeriac) selective reductions of the exocyclic carbonyl group.
Fil: Pergomet, Jorgelina Leonor. 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
Fil: Larghi, Enrique Leandro. 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
Fil: Kaufman, Teodoro Saul. 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
Fil: Bracca, Andrea Beatriz Juana. 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
Total synthesis
Heterocyclic natural product
Benzofuran-3-one
Biotransformation
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:11336/63879
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/63879
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling First total synthesis of the only known 2-isopropyliden-2: H -benzofuran-3-one isolated from V. luetzelburgiiPergomet, Jorgelina LeonorLarghi, Enrique LeandroKaufman, Teodoro SaulBracca, Andrea Beatriz JuanaTotal synthesisHeterocyclic natural productBenzofuran-3-oneBiotransformationhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1The first total synthesis of 5-(1-hydroxy-1-ethyl)-2-isopropyliden-2H-benzofuran-3-one, is reported in its racemic and in one of its optically active [(S)-(-)] forms. This heterocycle, isolated from Verbesina luetzelburgii, is the only known 2-isopropyliden-2H-benzofuran-3-one produced by species of Verbesina. The sequence took place in eight steps and 19% overall yield (up to 33% for the chiral form), from 4′-hydroxyacetophenone. It entailed carbonyl group protection as the 1,3-dioxolane and a phenol ortho formylation, followed by a Williamson etherification with chloroacetone and an organocatalytic cross-aldolization, to afford a 2-acetyl-2,3-dihydrobenzofuran-3-ol intermediate. The latter underwent a methyl Grignard addition to the carbonyl moiety, followed by selective oxidation of the benzylic alcohol and deprotection, resulting in a β-hydroxy diketone derivative. A MsCl-assisted dehydration of the tertiary alcohol, established the isopropylidene motif, whereas the syntheses culminated by chemical or enzymatic (carrot, celeriac) selective reductions of the exocyclic carbonyl group.Fil: Pergomet, Jorgelina Leonor. 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; ArgentinaFil: Larghi, Enrique Leandro. 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; ArgentinaFil: Kaufman, Teodoro Saul. 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; ArgentinaFil: Bracca, Andrea Beatriz Juana. 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 Chemistry2017-01info: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/11336/63879Pergomet, Jorgelina Leonor; Larghi, Enrique Leandro; Kaufman, Teodoro Saul; Bracca, Andrea Beatriz Juana; First total synthesis of the only known 2-isopropyliden-2: H -benzofuran-3-one isolated from V. luetzelburgii; Royal Society of Chemistry; RSC Advances; 7; 9; 1-2017; 5242-52502046-2069CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1039/c6ra28587binfo:eu-repo/semantics/altIdentifier/url/https://pubs.rsc.org/en/Content/ArticleLanding/2017/RA/C6RA28587Binfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T10:42:28Zoai:ri.conicet.gov.ar:11336/63879instacron: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 10:42:29.013CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv First total synthesis of the only known 2-isopropyliden-2: H -benzofuran-3-one isolated from V. luetzelburgii
title First total synthesis of the only known 2-isopropyliden-2: H -benzofuran-3-one isolated from V. luetzelburgii
spellingShingle First total synthesis of the only known 2-isopropyliden-2: H -benzofuran-3-one isolated from V. luetzelburgii
Pergomet, Jorgelina Leonor
Total synthesis
Heterocyclic natural product
Benzofuran-3-one
Biotransformation
title_short First total synthesis of the only known 2-isopropyliden-2: H -benzofuran-3-one isolated from V. luetzelburgii
title_full First total synthesis of the only known 2-isopropyliden-2: H -benzofuran-3-one isolated from V. luetzelburgii
title_fullStr First total synthesis of the only known 2-isopropyliden-2: H -benzofuran-3-one isolated from V. luetzelburgii
title_full_unstemmed First total synthesis of the only known 2-isopropyliden-2: H -benzofuran-3-one isolated from V. luetzelburgii
title_sort First total synthesis of the only known 2-isopropyliden-2: H -benzofuran-3-one isolated from V. luetzelburgii
dc.creator.none.fl_str_mv Pergomet, Jorgelina Leonor
Larghi, Enrique Leandro
Kaufman, Teodoro Saul
Bracca, Andrea Beatriz Juana
author Pergomet, Jorgelina Leonor
author_facet Pergomet, Jorgelina Leonor
Larghi, Enrique Leandro
Kaufman, Teodoro Saul
Bracca, Andrea Beatriz Juana
author_role author
author2 Larghi, Enrique Leandro
Kaufman, Teodoro Saul
Bracca, Andrea Beatriz Juana
author2_role author
author
author
dc.subject.none.fl_str_mv Total synthesis
Heterocyclic natural product
Benzofuran-3-one
Biotransformation
topic Total synthesis
Heterocyclic natural product
Benzofuran-3-one
Biotransformation
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv The first total synthesis of 5-(1-hydroxy-1-ethyl)-2-isopropyliden-2H-benzofuran-3-one, is reported in its racemic and in one of its optically active [(S)-(-)] forms. This heterocycle, isolated from Verbesina luetzelburgii, is the only known 2-isopropyliden-2H-benzofuran-3-one produced by species of Verbesina. The sequence took place in eight steps and 19% overall yield (up to 33% for the chiral form), from 4′-hydroxyacetophenone. It entailed carbonyl group protection as the 1,3-dioxolane and a phenol ortho formylation, followed by a Williamson etherification with chloroacetone and an organocatalytic cross-aldolization, to afford a 2-acetyl-2,3-dihydrobenzofuran-3-ol intermediate. The latter underwent a methyl Grignard addition to the carbonyl moiety, followed by selective oxidation of the benzylic alcohol and deprotection, resulting in a β-hydroxy diketone derivative. A MsCl-assisted dehydration of the tertiary alcohol, established the isopropylidene motif, whereas the syntheses culminated by chemical or enzymatic (carrot, celeriac) selective reductions of the exocyclic carbonyl group.
Fil: Pergomet, Jorgelina Leonor. 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
Fil: Larghi, Enrique Leandro. 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
Fil: Kaufman, Teodoro Saul. 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
Fil: Bracca, Andrea Beatriz Juana. 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 The first total synthesis of 5-(1-hydroxy-1-ethyl)-2-isopropyliden-2H-benzofuran-3-one, is reported in its racemic and in one of its optically active [(S)-(-)] forms. This heterocycle, isolated from Verbesina luetzelburgii, is the only known 2-isopropyliden-2H-benzofuran-3-one produced by species of Verbesina. The sequence took place in eight steps and 19% overall yield (up to 33% for the chiral form), from 4′-hydroxyacetophenone. It entailed carbonyl group protection as the 1,3-dioxolane and a phenol ortho formylation, followed by a Williamson etherification with chloroacetone and an organocatalytic cross-aldolization, to afford a 2-acetyl-2,3-dihydrobenzofuran-3-ol intermediate. The latter underwent a methyl Grignard addition to the carbonyl moiety, followed by selective oxidation of the benzylic alcohol and deprotection, resulting in a β-hydroxy diketone derivative. A MsCl-assisted dehydration of the tertiary alcohol, established the isopropylidene motif, whereas the syntheses culminated by chemical or enzymatic (carrot, celeriac) selective reductions of the exocyclic carbonyl group.
publishDate 2017
dc.date.none.fl_str_mv 2017-01
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/11336/63879
Pergomet, Jorgelina Leonor; Larghi, Enrique Leandro; Kaufman, Teodoro Saul; Bracca, Andrea Beatriz Juana; First total synthesis of the only known 2-isopropyliden-2: H -benzofuran-3-one isolated from V. luetzelburgii; Royal Society of Chemistry; RSC Advances; 7; 9; 1-2017; 5242-5250
2046-2069
CONICET Digital
CONICET
url http://hdl.handle.net/11336/63879
identifier_str_mv Pergomet, Jorgelina Leonor; Larghi, Enrique Leandro; Kaufman, Teodoro Saul; Bracca, Andrea Beatriz Juana; First total synthesis of the only known 2-isopropyliden-2: H -benzofuran-3-one isolated from V. luetzelburgii; Royal Society of Chemistry; RSC Advances; 7; 9; 1-2017; 5242-5250
2046-2069
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1039/c6ra28587b
info:eu-repo/semantics/altIdentifier/url/https://pubs.rsc.org/en/Content/ArticleLanding/2017/RA/C6RA28587B
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
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
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score 13.070432

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