Photochemical insights on acyl azolium salts enable the design of a tandem hydrogen atom transfer/halogen atom transfer acylation of alkyl bromides and chlorides

Acyl azolium salts have been recently described as good HAT mediators in their excited state-similarly to diaryl ketones-and good acylating reagents, with the beneficial property of enabling incorporation of the acyl residue into the final molecule. Nevertheless, despite significant synthetic effort...

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Authors: MacLean, Ian, Grenda, Daniel Jan, Echávarri, Elena, Muth, Stephan, Nuernberger, Patrick, Marzo, Leyre
Format: article
Publication Date:2025
Country:España
Institution:Universidad Autónoma de Madrid
Repository:Biblos-e Archivo. Repositorio Institucional de la UAM
Language:English
OAI Identifier:oai:repositorio.uam.es:10486/729600
Online Access:https://hdl.handle.net/10486/729600
https://dx.doi.org/10.1021/jacs.5c10923
Access Level:Open access
Keyword:Acylation
Atoms
Electronic properties
Hydrogen
Química
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spelling Photochemical insights on acyl azolium salts enable the design of a tandem hydrogen atom transfer/halogen atom transfer acylation of alkyl bromides and chloridesMacLean, IanGrenda, Daniel JanEchávarri, ElenaMuth, StephanNuernberger, PatrickMarzo, LeyreAcylationAtomsElectronic propertiesHydrogenQuímicaAcyl azolium salts have been recently described as good HAT mediators in their excited state-similarly to diaryl ketones-and good acylating reagents, with the beneficial property of enabling incorporation of the acyl residue into the final molecule. Nevertheless, despite significant synthetic efforts in the field, knowledge and understanding of the key reactive intermediates especially through spectroscopic investigations remain elusive. Herein, we present a photochemical study of the reactivity of acyl azolium salts that comprises the detection and characterization of the triplet excited state and the decisive ketyl radical intermediate. Moreover, this mechanistic insight allowed us the development of an alternative method based on a silane-mediated tandem HAT/XAT activation strategy that enables not only the acylation of alkyl bromides but also the acylation of the more challenging alkyl chlorides. The method has proven to be efficient, regardless of the electronic properties of the acyl azolium or the substituents present in the alkyl halide. Furthermore, its robustness has been proven through the functionalization of natural product derivatives either as acyl azolium or alkyl bromide derivativesFinancial support was provided by the Spanish Government (PID2023-146050NA-I00) and by the Deutsche Forschungsgemeinschaft (DFG, German Science Foundation) within TRR 325-444632635 (project A5). I. M. thanks CAM for his predoctoral fellowship (PIPF-2023/ECO-30898) and L.M. thanks the Spanish Government for a Ramón y Cajal contract (RYC2021-031590-I) and the Alexander von Humbold foundation for the 3 months renewed research stay. We would like to acknowledge the Interdepartmental Research Service (SIdI) at UAM for providing access to and the use of their scientific equipmentACSDepartamento de Química OrgánicaFacultad de Ciencias20252025-08-14research articlehttp://purl.org/coar/resource_type/c_2df8fbb1VoRhttp://purl.org/coar/version/c_970fb48d4fbd8a85info:eu-repo/semantics/articleapplication/pdfhttps://hdl.handle.net/10486/729600https://dx.doi.org/10.1021/jacs.5c10923reponame:Biblos-e Archivo. Repositorio Institucional de la UAMinstname:Universidad Autónoma de MadridInglésengopen accesshttp://purl.org/coar/access_right/c_abf2Attribution 4.0 Internationalhttp://creativecommons.org/licenses/by/4.0/info:eu-repo/semantics/openAccessoai:repositorio.uam.es:10486/7296002026-06-23T12:46:27Z
dc.title.none.fl_str_mv Photochemical insights on acyl azolium salts enable the design of a tandem hydrogen atom transfer/halogen atom transfer acylation of alkyl bromides and chlorides
title Photochemical insights on acyl azolium salts enable the design of a tandem hydrogen atom transfer/halogen atom transfer acylation of alkyl bromides and chlorides
spellingShingle Photochemical insights on acyl azolium salts enable the design of a tandem hydrogen atom transfer/halogen atom transfer acylation of alkyl bromides and chlorides
MacLean, Ian
Acylation
Atoms
Electronic properties
Hydrogen
Química
title_short Photochemical insights on acyl azolium salts enable the design of a tandem hydrogen atom transfer/halogen atom transfer acylation of alkyl bromides and chlorides
title_full Photochemical insights on acyl azolium salts enable the design of a tandem hydrogen atom transfer/halogen atom transfer acylation of alkyl bromides and chlorides
title_fullStr Photochemical insights on acyl azolium salts enable the design of a tandem hydrogen atom transfer/halogen atom transfer acylation of alkyl bromides and chlorides
title_full_unstemmed Photochemical insights on acyl azolium salts enable the design of a tandem hydrogen atom transfer/halogen atom transfer acylation of alkyl bromides and chlorides
title_sort Photochemical insights on acyl azolium salts enable the design of a tandem hydrogen atom transfer/halogen atom transfer acylation of alkyl bromides and chlorides
dc.creator.none.fl_str_mv MacLean, Ian
Grenda, Daniel Jan
Echávarri, Elena
Muth, Stephan
Nuernberger, Patrick
Marzo, Leyre
author MacLean, Ian
author_facet MacLean, Ian
Grenda, Daniel Jan
Echávarri, Elena
Muth, Stephan
Nuernberger, Patrick
Marzo, Leyre
author_role author
author2 Grenda, Daniel Jan
Echávarri, Elena
Muth, Stephan
Nuernberger, Patrick
Marzo, Leyre
author2_role author
author
author
author
author
dc.contributor.none.fl_str_mv Departamento de Química Orgánica
Facultad de Ciencias
dc.subject.none.fl_str_mv Acylation
Atoms
Electronic properties
Hydrogen
Química
topic Acylation
Atoms
Electronic properties
Hydrogen
Química
description Acyl azolium salts have been recently described as good HAT mediators in their excited state-similarly to diaryl ketones-and good acylating reagents, with the beneficial property of enabling incorporation of the acyl residue into the final molecule. Nevertheless, despite significant synthetic efforts in the field, knowledge and understanding of the key reactive intermediates especially through spectroscopic investigations remain elusive. Herein, we present a photochemical study of the reactivity of acyl azolium salts that comprises the detection and characterization of the triplet excited state and the decisive ketyl radical intermediate. Moreover, this mechanistic insight allowed us the development of an alternative method based on a silane-mediated tandem HAT/XAT activation strategy that enables not only the acylation of alkyl bromides but also the acylation of the more challenging alkyl chlorides. The method has proven to be efficient, regardless of the electronic properties of the acyl azolium or the substituents present in the alkyl halide. Furthermore, its robustness has been proven through the functionalization of natural product derivatives either as acyl azolium or alkyl bromide derivatives
publishDate 2025
dc.date.none.fl_str_mv 2025
2025-08-14
dc.type.none.fl_str_mv research article
http://purl.org/coar/resource_type/c_2df8fbb1
VoR
http://purl.org/coar/version/c_970fb48d4fbd8a85
dc.type.openaire.fl_str_mv info:eu-repo/semantics/article
format article
dc.identifier.none.fl_str_mv https://hdl.handle.net/10486/729600
https://dx.doi.org/10.1021/jacs.5c10923
url https://hdl.handle.net/10486/729600
https://dx.doi.org/10.1021/jacs.5c10923
dc.language.none.fl_str_mv Inglés
eng
language_invalid_str_mv Inglés
language eng
dc.rights.none.fl_str_mv open access
http://purl.org/coar/access_right/c_abf2
Attribution 4.0 International
http://creativecommons.org/licenses/by/4.0/
dc.rights.openaire.fl_str_mv info:eu-repo/semantics/openAccess
rights_invalid_str_mv open access
http://purl.org/coar/access_right/c_abf2
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 ACS
publisher.none.fl_str_mv ACS
dc.source.none.fl_str_mv reponame:Biblos-e Archivo. Repositorio Institucional de la UAM
instname:Universidad Autónoma de Madrid
instname_str Universidad Autónoma de Madrid
reponame_str Biblos-e Archivo. Repositorio Institucional de la UAM
collection Biblos-e Archivo. Repositorio Institucional de la UAM
repository.name.fl_str_mv
repository.mail.fl_str_mv
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