Balancing acceleration and turnover in [1 + 1] tetra-imine bis-calix[4]pyrrole reactor for Huisgen cycloadditions

Tailored molecular cages can confine reactive partners and enhance their reaction rates. However, for bimolecular reactions, product inhibition is commonly observed. We report a tetra-imine bis-calix[4]pyrrole cage with two chemically non-equivalent polar hemispheres that promote azide-alkyne Huisge...

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Detalles Bibliográficos
Autores: Li, Yifan, Aragay, Gemma, Ballester, Pablo
Tipo de recurso: artículo
Fecha de publicación:2026
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:dnet:recercat____::b068a258b1dad28a8ea2d3eb873905f6
Acceso en línea:https://hdl.handle.net/2072/489522
https://doi.org/10.1038/s41467-026-72315-w
Access Level:acceso abierto
Palabra clave:Química
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spelling Balancing acceleration and turnover in [1 + 1] tetra-imine bis-calix[4]pyrrole reactor for Huisgen cycloadditionsLi, YifanAragay, GemmaBallester, PabloQuímica54Tailored molecular cages can confine reactive partners and enhance their reaction rates. However, for bimolecular reactions, product inhibition is commonly observed. We report a tetra-imine bis-calix[4]pyrrole cage with two chemically non-equivalent polar hemispheres that promote azide-alkyne Huisgen cycloadditions. This cage forms 1:1 and 1:2 complexes with para-substituted pyridine-N-oxides, including ternary hetero-complexes with an azide and an alkyne moiety into proximity. Here, we show that cage confinement accelerates the regioselective formation of 1,4-triazoles. A global kinetic model allows the determination of the intra-vessel rate constant (kintra) without direct quantification of the “Michaelis” ternary complex. Modest acceleration is observed for one pair of reactants, yet the cage can still turn over because the product is weakly bound. Extending the azide linker by one methylene dramatically enhances acceleration and introduces product inhibition. Comparisons with a related octa-imine cage reveal how subtle geometric changes tune the balance between transition-state stabilization and product release.info:eu-repo/semantics/acceptedVersionSpringer Nature2026info:eu-repo/semantics/article12 p.application/pdfhttps://hdl.handle.net/2072/489522https://doi.org/10.1038/s41467-026-72315-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)InglésGobierno de España MICIU/AEI/10.13039/501100011033, FEDER/UE (PID2023-149233NB-I00) and MICIU/AEI/10.13039/501100011033 (Severo Ochoa Excellence Accreditations CEX2019-000925-S and CEX2024-001469-S)CERCA Program/Generalitat de CatalunyaAGAUR (2021 SGR 00851)ICIQ FoundationAttribution 4.0 Internationalhttp://creativecommons.org/licenses/by/4.0/info:eu-repo/semantics/openAccessoai:dnet:recercat____::b068a258b1dad28a8ea2d3eb873905f62026-05-29T05:05:01Z
dc.title.none.fl_str_mv Balancing acceleration and turnover in [1 + 1] tetra-imine bis-calix[4]pyrrole reactor for Huisgen cycloadditions
title Balancing acceleration and turnover in [1 + 1] tetra-imine bis-calix[4]pyrrole reactor for Huisgen cycloadditions
spellingShingle Balancing acceleration and turnover in [1 + 1] tetra-imine bis-calix[4]pyrrole reactor for Huisgen cycloadditions
Li, Yifan
Química
54
title_short Balancing acceleration and turnover in [1 + 1] tetra-imine bis-calix[4]pyrrole reactor for Huisgen cycloadditions
title_full Balancing acceleration and turnover in [1 + 1] tetra-imine bis-calix[4]pyrrole reactor for Huisgen cycloadditions
title_fullStr Balancing acceleration and turnover in [1 + 1] tetra-imine bis-calix[4]pyrrole reactor for Huisgen cycloadditions
title_full_unstemmed Balancing acceleration and turnover in [1 + 1] tetra-imine bis-calix[4]pyrrole reactor for Huisgen cycloadditions
title_sort Balancing acceleration and turnover in [1 + 1] tetra-imine bis-calix[4]pyrrole reactor for Huisgen cycloadditions
dc.creator.none.fl_str_mv Li, Yifan
Aragay, Gemma
Ballester, Pablo
author Li, Yifan
author_facet Li, Yifan
Aragay, Gemma
Ballester, Pablo
author_role author
author2 Aragay, Gemma
Ballester, Pablo
author2_role author
author
dc.subject.none.fl_str_mv Química
54
topic Química
54
description Tailored molecular cages can confine reactive partners and enhance their reaction rates. However, for bimolecular reactions, product inhibition is commonly observed. We report a tetra-imine bis-calix[4]pyrrole cage with two chemically non-equivalent polar hemispheres that promote azide-alkyne Huisgen cycloadditions. This cage forms 1:1 and 1:2 complexes with para-substituted pyridine-N-oxides, including ternary hetero-complexes with an azide and an alkyne moiety into proximity. Here, we show that cage confinement accelerates the regioselective formation of 1,4-triazoles. A global kinetic model allows the determination of the intra-vessel rate constant (kintra) without direct quantification of the “Michaelis” ternary complex. Modest acceleration is observed for one pair of reactants, yet the cage can still turn over because the product is weakly bound. Extending the azide linker by one methylene dramatically enhances acceleration and introduces product inhibition. Comparisons with a related octa-imine cage reveal how subtle geometric changes tune the balance between transition-state stabilization and product release.
publishDate 2026
dc.date.none.fl_str_mv 2026
dc.type.none.fl_str_mv info:eu-repo/semantics/article
format article
dc.identifier.none.fl_str_mv https://hdl.handle.net/2072/489522
https://doi.org/10.1038/s41467-026-72315-w
url https://hdl.handle.net/2072/489522
https://doi.org/10.1038/s41467-026-72315-w
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv Gobierno de España MICIU/AEI/10.13039/501100011033, FEDER/UE (PID2023-149233NB-I00) and MICIU/AEI/10.13039/501100011033 (Severo Ochoa Excellence Accreditations CEX2019-000925-S and CEX2024-001469-S)
CERCA Program/Generalitat de Catalunya
AGAUR (2021 SGR 00851)
ICIQ Foundation
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 12 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 15,812429

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