Dearomative syn-Dihydroxylation of Naphthalenes with a Biomimetic Iron Catalyst

Arenes are interesting feedstocks for organic synthesis because of their natural abundance. However, the stability conferred by aromaticity severely limits their reactivity, mostly to reactions where aromaticity is retained. Methods for oxidative dearomatization of unactivated arenes are exceedingly...

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Detalles Bibliográficos
Autores: Choukairi Afailal, Najoua, Borrell Recasens, Margarida, Cianfanelli, Marco, Costas Salgueiro, Miquel
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:2023
País:España
Institución:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
Repositorio:Recercat. Dipósit de la Recerca de Catalunya
OAI Identifier:oai:recercat.cat:10256/24633
Acceso en línea:http://hdl.handle.net/10256/24633
Access Level:acceso abierto
Palabra clave:Catalitzadors
Catalysts
Compostos aromàtics
Aromatic compounds
Oxidació
Oxidation
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spelling Dearomative syn-Dihydroxylation of Naphthalenes with a Biomimetic Iron CatalystChoukairi Afailal, NajouaBorrell Recasens, MargaridaCianfanelli, MarcoCostas Salgueiro, MiquelCatalitzadorsCatalystsCompostos aromàticsAromatic compoundsOxidacióOxidationArenes are interesting feedstocks for organic synthesis because of their natural abundance. However, the stability conferred by aromaticity severely limits their reactivity, mostly to reactions where aromaticity is retained. Methods for oxidative dearomatization of unactivated arenes are exceedingly rare but particularly valuable because the introduction of Csp3–O bonds transforms the flat aromatic ring in 3D skeletons and confers the oxygenated molecules with a very rich chemistry suitable for diversification. Mimicking the activity of naphthalene dioxygenase (NDO), a non-heme iron-dependent bacterial enzyme, herein we describe the catalytic syn-dihydroxylation of naphthalenes with hydrogen peroxide, employing a sterically encumbered and exceedingly reactive yet chemoselective iron catalyst. The high electrophilicity of hypervalent iron oxo species is devised as a key to enabling overcoming the aromatically promoted kinetic stability. Interestingly, the first dihydroxylation of the arene renders a reactive olefinic site ready for further dihydroxylation. Sequential bis-dihydroxylation of a broad range of naphthalenes provides valuable tetrahydroxylated products in preparative yields, amenable for rapid diversificationOpen Access funding provided thanks to the CRUE-CSIC agreement with American Chemical Society (ACS)American Chemical Society (ACS)2023info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionpeer-reviewedapplication/pdfhttp://hdl.handle.net/10256/24633http://hdl.handle.net/10256/24633Journal of the American Chemical Society (JACS), 2024, vol. 146, núm. 1, p. 240-249Articles publicats (D-Q)reponame:Recercat. Dipósit de la Recerca de Catalunyainstname:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)Inglésinfo:eu-repo/semantics/altIdentifier/doi/10.1021/jacs.3c08565info:eu-repo/semantics/altIdentifier/issn/0002-7863info:eu-repo/semantics/altIdentifier/eissn/1520-5126Attribution 4.0 Internationalhttp://creativecommons.org/licenses/by/4.0/info:eu-repo/semantics/openAccessoai:recercat.cat:10256/246332026-05-29T05:05:01Z
dc.title.none.fl_str_mv Dearomative syn-Dihydroxylation of Naphthalenes with a Biomimetic Iron Catalyst
title Dearomative syn-Dihydroxylation of Naphthalenes with a Biomimetic Iron Catalyst
spellingShingle Dearomative syn-Dihydroxylation of Naphthalenes with a Biomimetic Iron Catalyst
Choukairi Afailal, Najoua
Catalitzadors
Catalysts
Compostos aromàtics
Aromatic compounds
Oxidació
Oxidation
title_short Dearomative syn-Dihydroxylation of Naphthalenes with a Biomimetic Iron Catalyst
title_full Dearomative syn-Dihydroxylation of Naphthalenes with a Biomimetic Iron Catalyst
title_fullStr Dearomative syn-Dihydroxylation of Naphthalenes with a Biomimetic Iron Catalyst
title_full_unstemmed Dearomative syn-Dihydroxylation of Naphthalenes with a Biomimetic Iron Catalyst
title_sort Dearomative syn-Dihydroxylation of Naphthalenes with a Biomimetic Iron Catalyst
dc.creator.none.fl_str_mv Choukairi Afailal, Najoua
Borrell Recasens, Margarida
Cianfanelli, Marco
Costas Salgueiro, Miquel
author Choukairi Afailal, Najoua
author_facet Choukairi Afailal, Najoua
Borrell Recasens, Margarida
Cianfanelli, Marco
Costas Salgueiro, Miquel
author_role author
author2 Borrell Recasens, Margarida
Cianfanelli, Marco
Costas Salgueiro, Miquel
author2_role author
author
author
dc.subject.none.fl_str_mv Catalitzadors
Catalysts
Compostos aromàtics
Aromatic compounds
Oxidació
Oxidation
topic Catalitzadors
Catalysts
Compostos aromàtics
Aromatic compounds
Oxidació
Oxidation
description Arenes are interesting feedstocks for organic synthesis because of their natural abundance. However, the stability conferred by aromaticity severely limits their reactivity, mostly to reactions where aromaticity is retained. Methods for oxidative dearomatization of unactivated arenes are exceedingly rare but particularly valuable because the introduction of Csp3–O bonds transforms the flat aromatic ring in 3D skeletons and confers the oxygenated molecules with a very rich chemistry suitable for diversification. Mimicking the activity of naphthalene dioxygenase (NDO), a non-heme iron-dependent bacterial enzyme, herein we describe the catalytic syn-dihydroxylation of naphthalenes with hydrogen peroxide, employing a sterically encumbered and exceedingly reactive yet chemoselective iron catalyst. The high electrophilicity of hypervalent iron oxo species is devised as a key to enabling overcoming the aromatically promoted kinetic stability. Interestingly, the first dihydroxylation of the arene renders a reactive olefinic site ready for further dihydroxylation. Sequential bis-dihydroxylation of a broad range of naphthalenes provides valuable tetrahydroxylated products in preparative yields, amenable for rapid diversification
publishDate 2023
dc.date.none.fl_str_mv 2023
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
peer-reviewed
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/10256/24633
http://hdl.handle.net/10256/24633
url http://hdl.handle.net/10256/24633
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1021/jacs.3c08565
info:eu-repo/semantics/altIdentifier/issn/0002-7863
info:eu-repo/semantics/altIdentifier/eissn/1520-5126
dc.rights.none.fl_str_mv Attribution 4.0 International
http://creativecommons.org/licenses/by/4.0/
info:eu-repo/semantics/openAccess
rights_invalid_str_mv Attribution 4.0 International
http://creativecommons.org/licenses/by/4.0/
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv American Chemical Society (ACS)
publisher.none.fl_str_mv American Chemical Society (ACS)
dc.source.none.fl_str_mv Journal of the American Chemical Society (JACS), 2024, vol. 146, núm. 1, p. 240-249
Articles publicats (D-Q)
reponame:Recercat. Dipósit de la Recerca de Catalunya
instname:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
instname_str Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
reponame_str Recercat. Dipósit de la Recerca de Catalunya
collection Recercat. Dipósit de la Recerca de Catalunya
repository.name.fl_str_mv
repository.mail.fl_str_mv
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