Hexafluoroisopropanol-assisted selective intramolecular synthesis of heterocycles by single-electron transfer

Intramolecular amination of remote aliphatic C–H bonds via hydrogen-atom transfer reactions has become a powerful tool for accessing saturated nitrogen-containing heterocycles. However, the formation of six-membered rings or oxa-heterocycles remains a formidable challenge for Hofmann–Löffler–Freytag...

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Detalhes bibliográficos
Autores: Xie, Jiale, Zhang, Jiayu, Kasemthaveechok, Sitthichok, Lopez-Resano, Sara, Cots, Eric, Maseras, Feliu, Perez-Temprano, Monica H.
Formato: artículo
Estado:Versión publicada
Fecha de publicación:2024
País:España
Recursos: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:2072/537730
Acesso em linha:http://hdl.handle.net/2072/537730
https://doi.org/10.1038/s44160-024-00566-w
Access Level:acceso abierto
Palavra-chave:Química
54 - Química
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spelling Hexafluoroisopropanol-assisted selective intramolecular synthesis of heterocycles by single-electron transferXie, JialeZhang, JiayuKasemthaveechok, SitthichokLopez-Resano, SaraCots, EricMaseras, FeliuPerez-Temprano, Monica H.Química54 - QuímicaIntramolecular amination of remote aliphatic C–H bonds via hydrogen-atom transfer reactions has become a powerful tool for accessing saturated nitrogen-containing heterocycles. However, the formation of six-membered rings or oxa-heterocycles remains a formidable challenge for Hofmann–Löffler–Freytag reactions. Here we show how by simply combining bench-stable (bis(trifluoroacetoxy)iodo)benzene and hexafluoroisopropanol (HFIP) we can switch from the well-established Hofmann–Löffler–Freytag mechanism to a different versatile reaction pathway that enables selective C(sp3)–H bond functionalization. We have exploited the facile formation of radical cations via single-electron transfer, in the presence or absence of light, to synthesize pyrrolidines and piperidines, including drug-type molecules, along with O-heterocycles. Experimental and computational mechanistic studies support two distinct mechanistic pathways, depending on the electron density of the substrate, in which the HFIP plays a multifunctional role.Springer Nature2024info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersion10 p.application/pdfhttp://hdl.handle.net/2072/537730https://doi.org/10.1038/s44160-024-00566-wRECERCAT (Dipòsit de la Recerca de Catalunya)reponame:Recercat. Dipósit de la Recerca de Catalunyainstname:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)InglésICIQ, CERCA Programme/Generalitat de CatalunyaMinisterio de Ciencia e Innovación/Agencia Estatal de Investigación (MICINN/AEI/Severo Ochoa Excellence Accreditation 2020-2023–CEX2019-000925-S; grant numbers PID2020-112733GB-I00, PID2020-112825RB-I00)Agencia de Gestión de Ayudas Universitarias y de Investigación (AGAUR) 2021 SGR 01154J.X. and J.Z. thank the China Scholarship Council for predoctoral fellowships (CSC202108330066 and CSC201906280437)S.L.-R. thanks the Generalitat de Catalunya for an FI–Agaur predoctoral contract.CC-BY-4.0info:eu-repo/semantics/openAccessoai:recercat.cat:2072/5377302026-05-29T05:05:01Z
dc.title.none.fl_str_mv Hexafluoroisopropanol-assisted selective intramolecular synthesis of heterocycles by single-electron transfer
title Hexafluoroisopropanol-assisted selective intramolecular synthesis of heterocycles by single-electron transfer
spellingShingle Hexafluoroisopropanol-assisted selective intramolecular synthesis of heterocycles by single-electron transfer
Xie, Jiale
Química
54 - Química
title_short Hexafluoroisopropanol-assisted selective intramolecular synthesis of heterocycles by single-electron transfer
title_full Hexafluoroisopropanol-assisted selective intramolecular synthesis of heterocycles by single-electron transfer
title_fullStr Hexafluoroisopropanol-assisted selective intramolecular synthesis of heterocycles by single-electron transfer
title_full_unstemmed Hexafluoroisopropanol-assisted selective intramolecular synthesis of heterocycles by single-electron transfer
title_sort Hexafluoroisopropanol-assisted selective intramolecular synthesis of heterocycles by single-electron transfer
dc.creator.none.fl_str_mv Xie, Jiale
Zhang, Jiayu
Kasemthaveechok, Sitthichok
Lopez-Resano, Sara
Cots, Eric
Maseras, Feliu
Perez-Temprano, Monica H.
author Xie, Jiale
author_facet Xie, Jiale
Zhang, Jiayu
Kasemthaveechok, Sitthichok
Lopez-Resano, Sara
Cots, Eric
Maseras, Feliu
Perez-Temprano, Monica H.
author_role author
author2 Zhang, Jiayu
Kasemthaveechok, Sitthichok
Lopez-Resano, Sara
Cots, Eric
Maseras, Feliu
Perez-Temprano, Monica H.
author2_role author
author
author
author
author
author
dc.subject.none.fl_str_mv Química
54 - Química
topic Química
54 - Química
description Intramolecular amination of remote aliphatic C–H bonds via hydrogen-atom transfer reactions has become a powerful tool for accessing saturated nitrogen-containing heterocycles. However, the formation of six-membered rings or oxa-heterocycles remains a formidable challenge for Hofmann–Löffler–Freytag reactions. Here we show how by simply combining bench-stable (bis(trifluoroacetoxy)iodo)benzene and hexafluoroisopropanol (HFIP) we can switch from the well-established Hofmann–Löffler–Freytag mechanism to a different versatile reaction pathway that enables selective C(sp3)–H bond functionalization. We have exploited the facile formation of radical cations via single-electron transfer, in the presence or absence of light, to synthesize pyrrolidines and piperidines, including drug-type molecules, along with O-heterocycles. Experimental and computational mechanistic studies support two distinct mechanistic pathways, depending on the electron density of the substrate, in which the HFIP plays a multifunctional role.
publishDate 2024
dc.date.none.fl_str_mv 2024
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/2072/537730
https://doi.org/10.1038/s44160-024-00566-w
url http://hdl.handle.net/2072/537730
https://doi.org/10.1038/s44160-024-00566-w
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv ICIQ, CERCA Programme/Generalitat de Catalunya
Ministerio de Ciencia e Innovación/Agencia Estatal de Investigación (MICINN/AEI/Severo Ochoa Excellence Accreditation 2020-2023–CEX2019-000925-S; grant numbers PID2020-112733GB-I00, PID2020-112825RB-I00)
Agencia de Gestión de Ayudas Universitarias y de Investigación (AGAUR) 2021 SGR 01154
J.X. and J.Z. thank the China Scholarship Council for predoctoral fellowships (CSC202108330066 and CSC201906280437)
S.L.-R. thanks the Generalitat de Catalunya for an FI–Agaur predoctoral contract.
dc.rights.none.fl_str_mv CC-BY-4.0
info:eu-repo/semantics/openAccess
rights_invalid_str_mv CC-BY-4.0
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv 10 p.
application/pdf
dc.publisher.none.fl_str_mv Springer Nature
publisher.none.fl_str_mv Springer Nature
dc.source.none.fl_str_mv RECERCAT (Dipòsit de la Recerca de Catalunya)
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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score 15,81155

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